Insecticidal compounds

ABSTRACT

A compound of formula (I): wherein A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , G 1 , G 2 , Q 1  and Q 2  are as defined in claim  1 ; or a salt or N-oxide thereof. Furthermore, the present invention relates to processes and intermediates for preparing compounds of formula (I), to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.

The present invention relates to certain aromatic bisamide derivatives,to processes and intermediates for preparing them, to insecticidal,acaricidal, molluscicidal and nematicidal compositions comprising themand to methods of using them to combat and control insect, acarine,mollusc and nematode pests.

Aromatic bisamide derivatives with insecticidal properties aredisclosed, for example, in EP 1,714,958, JP 2006/306771, WO 06/137376,WO 06/137395 and WO 07/017,075.

It has now surprisingly been found that certain aromatic bisamidederivatives which have at least one cyano, thiocyanato,aminothiocarbonyl, N—C₁-C₄alkyl-aminothiocarbonyl orN,N-di-C₁-C₄alkyl-aminothiocarbonyl substituent in the central aromaticring have insecticidal properties.

The present invention therefore provides a compound of formula (I):

whereinA¹, A², A³ and A⁴ are independently of one another C—R³, C—R⁵ ornitrogen, provided that at least one of A¹, A², A³ and A⁴ is C—R³ and nomore than two of A¹, A², A³ and A⁴ are nitrogen;R¹ and R² are independently of each other hydrogen, C₁-C₄alkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄alkylcarbonyl, hydroxy,C₁-C₄alkylcarbonyloxy, arylcarbonyloxy or arylcarbonyloxy wherein thearyl ring is substituted by one to five substituents independentlyselected from halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy orC₁-C₄haloalkoxy;G¹ and G² are independently of each other oxygen or sulfur;each R³ is independently cyano, thiocyanato, aminothiocarbonyl,N—C₁-C₄alkyl-aminothiocarbonyl or N,N-di-C₁-C₄alkyl-aminothiocarbonyl;each R⁵ is independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkylor C₁-C₄alkoxy;Q¹ is aryl or aryl substituted by one to five substituents R⁶, which maybe the same or different, or Q¹ is heterocyclyl or heterocyclylsubstituted by one to five substituents R⁶, which may be the same ordifferent; whereineach R⁶ is independently cyano, nitro, hydroxy, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₄alkoxy-C₁-C₄-alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₄alkoxy-C₁-C₄-alkoxy, C₁-C₆alkylthio,C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, N—C₁-C₆alkylamino,N,N-di-(C₁-C₆alkyl)amino, N,N-di-(C₁-C₆alkyl)aminocarbonyl,N,N-di-(C₁-C₆alkyl)aminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonylamino,aryl or aryl which is substituted by one to five substituentsindependently selected from cyano, nitro, hydroxy, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy, or heteroaryl orheteroaryl which is substituted by one to five substituentsindependently selected from cyano, nitro, hydroxy, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; andQ² is a moiety of formula (II) or (III)

whereinY¹ and Y⁵ are independently of each other cyano, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy-C₁-C₄-alkyl, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl or C₁-C₃haloalkylsulfonyl;Y³ is C₂-C₆ perfluoroalkyl, C₁-C₆ perfluoroalkylthio, C₁-C₆perfluoroalkylsulfinyl or C₁-C₆ perfluoroalkylsulfonyl;Y² and Y⁴ are independently of each other hydrogen, halogen orC₁-C₄alkyl;Y⁶ and Y⁹ are independently of each other cyano, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy-C₁-C₄-alkyl, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl or C₁-C₃haloalkylsulfonyl;Y⁸ is C₁-C₄haloalkoxy, C₂-C₆ perfluoroalkyl, C₁-C₆ perfluoroalkylthio,C₁-C₆ perfluoroalkylsulfinyl or C₁-C₆ perfluoroalkylsulfonyl;Y⁷ is hydrogen, halogen or C₁-C₄alkyl;or a salt or N-oxide thereof.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds.

Each alkyl moiety either alone or as part of a larger group (such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is a straight or branched chain and is, forexample, methyl, ethyl, n-propyl, n-butyl, iso-propyl, n-butyl,sec-butyl, iso-butyl or tert-butyl. The alkyl groups are preferably C₁to C₆ alkyl groups, more preferably C₁-C₄ and most preferably C₁-C₃alkyl groups.

Alkenyl and alkynyl moieties (either alone or as part of a larger group,such as alkenyloxy or alkynyloxy) can be in the form of straight orbranched chains, and the alkenyl moieties, where appropriate, can be ofeither the (E)- or (Z)-configuration. Examples are vinyl, allyl andpropargyl. The alkenyl and alkynyl groups are preferably C₂ to C₆alkenyl or alkynyl groups, more preferably C₂-C₄ and most preferablyC₂-C₃ alkenyl or alkynyl groups.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups (either alone or as part of a larger group, such ashaloalkoxy or haloalkylthio) are alkyl groups which are substituted withone or more of the same or different halogen atoms and are, for example,—CF₃, —CF₂Cl, —CH₂CF₃ or —CH₂CHF₂. Perfluoroalkyl groups (either aloneor as part of a larger group, such as perfluoroalkylthio) are aparticular type of haloalkyl group; they are alkyl groups which arecompletely substituted with fluorine atoms and are, for example, —CF₃,—CF₂CF₃ or —CF(CF₃)₂.

Haloalkenyl and haloalkynyl groups (either alone or as part of a largergroup, such as haloalkenyloxy or haloalkynyloxy) are alkenyl and alkynylgroups, respectively, which are substituted with one or more of the sameor different halogen atoms and are, for example, —CH═CF₂, —CCl═CClF or—CClC≡CH.

Cycloalkyl groups can be in mono- or bi-cyclic form and may optionallybe substituted by one or more methyl groups. The cycloalkyl groupspreferably contain 3 to 8 carbon atoms, more preferably 3 to 6 carbonatoms. Examples of monocyclic cycloalkyl groups are cyclopropyl,1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl.

Halocycloalkyl groups are cycloalkyl groups which are substituted withone or more of the same of different halogen atoms and may optionally besubstituted by one or more methyl groups. Examples of monocyclichalocycloalkyl groups are 2,2-dichloro-cyclopropyl,2,2-dichloro-1-methyl-cyclopropyl and 2-chloro-4-fluorocyclohexyl.

In the context of the present specification the term “aryl” refers to aring system which may be mono-, bi- or tricyclic. Examples of such ringsinclude phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. Apreferred aryl group is phenyl.

The term “heteroaryl” refers to an aromatic ring system containing atleast one heteroatom and consisting either of a single ring or of two ormore fused rings. Preferably, single rings will contain up to three andbicyclic systems up to four heteroatoms which will preferably be chosenfrom nitrogen, oxygen and sulfur. Examples of such groups includepyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, furanyl, thiophenyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.A preferred heteroaryl group is pyridine. Examples of bicyclic groupsare benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl,cinnolinyl and quinoxalinyl.

The term “heterocyclyl” is defined to include heteroaryl and in additiontheir unsaturated or partially unsaturated analogues such as4,5,6,7-tetrahydro-benzothiophenyl, 9H-fluorenyl,3,4-dihydro-2H-benzo-1,4-dioxepinyl, 2,3-dihydro-benzofuranyl,piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl,tetrahydrofuranyl and morpholinyl.

Preferred values of A¹, A², A³, R¹, R², G¹, G², R³, R⁵, Q¹, R⁶, Q², Y¹,Y², Y³, Y⁴, Y⁵, Y⁶, Y, Y⁸ and Y⁹ are, in any combination, as set outbelow.

Preferably A¹ is C—R³ or C—R⁵.

Preferably A² is C—R³ or C—R⁵.

Preferably A³ is C—R³ or C—R⁵.

Preferably A⁴ is C—R³ or C—R⁵.

Preferably one, two or three of A¹, A², A³ and A⁴ are C—R³.

More preferably one or two of A¹, A², A³ and A⁴ are C—R³.

Most preferably one of A¹, A², A³ and A⁴ is C—R³.

Preferably R¹ is hydrogen, methyl, ethyl, allyl, propargyl, acetyl,hydroxy, acetyloxy or benzoyloxy.

More preferably R¹ is hydrogen, methyl, ethyl, allyl, propargyl, acetylor hydroxy.

Even preferably R¹ is hydrogen, methyl or ethyl.

Yet even more preferably R¹ is hydrogen or methyl.

Most preferably R¹ is hydrogen.

Preferably R² is hydrogen, methyl, ethyl, allyl, propargyl, acetyl,hydroxy, acetyloxy or benzoyloxy.

More preferably R² is hydrogen, methyl, ethyl, allyl, propargyl, acetylor hydroxy.

Even preferably R² is hydrogen, methyl or ethyl.

Yet even more preferably R² is hydrogen or methyl.

Most preferably R² is hydrogen.

Preferably G¹ is oxygen.

Preferably G² is oxygen.

Preferably each R³ is independently cyano, thiocyanato oraminothiocarbonyl.

More preferably each R³ is independently cyano or thiocyanato.

Most preferably each R³ is cyano.

Preferably each R⁵ is independently hydrogen, fluoro, chloro, bromo,methyl, trifluoromethyl or methoxy.

More preferably each R⁵ is independently hydrogen, fluoro, chloro,bromo, methyl or trifluoromethyl.

Even more preferably each R⁵ is independently hydrogen, fluoro, methylor trifluoromethyl.

Yet even more preferably each R⁵ is independently hydrogen or fluoro.

Most preferably each R⁵ is hydrogen.

Preferably Q¹ is aryl or aryl substituted by one to five substituentsR⁶, which may be the same or different, or Q¹ is heteroaryl orheteroaryl substituted by one to five substituents R⁶, which may be thesame or different.

More preferably Q¹ is phenyl, pyridyl, furanyl, thiophenyl, pyrazolyl or1,2,3-thiadiazolyl, or phenyl, pyridyl, furanyl, thiophenyl, pyrazolylor 1,2,3-thiadiazolyl substituted by one to four substituentsindependently selected from cyano, nitro, hydroxy, bromo, chloro,fluoro, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio,methylsulfinyl, methylsulfonyl or phenyl. Examples of such morepreferred groups for Q¹ are 5-bromo-furan-2-yl, 2-bromo-phenyl,5-bromo-pyrid-3-yl, 2-chloro-4-fluoro-phenyl, 3-chloro-2-fluoro-phenyl,5-chloro-2-fluoro-phenyl, 3-chloro-2-methyl-phenyl,2-chloro-4-nitro-phenyl, 2-chloro-5-nitro-phenyl, 2-chloro-phenyl,3-chloro-phenyl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl,6-chloro-pyrid-3-yl, 5-chloro-thiophen-2-yl,3-chloro-5-trifluoromethyl-pyrid-2-yl, 4-cyano-2-fluoro-phenyl,4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl,1,3-dimethyl-1H-pyrazol-5-yl, 2-fluoro-phenyl, 4-fluoro-phenyl,2-fluoro-pyrid-3-yl, 2-fluoro-3-trifluoromethyl-phenyl,2-fluoro-5-trifluoromethyl-phenyl, 4-fluoro-3-trifluoromethyl-phenyl,furan-2-yl, 2-methoxy-phenyl, 2-methyl-phenyl, 3-methyl-pyrid-2-yl,4-methyl-1,2,3-thiadiazol-5-yl, 4-methylthio-phenyl,2-methylthio-pyrid-3-yl, 4-nitro-phenyl, phenyl, pyrid-3-yl, pyrid-4-yl,1,2,3-thiadiazol-4-yl, thiophen-2-yl, 2-trifluoromethoxy-phenyl,4-trifluoromethoxy-phenyl, 2-trifluoromethyl-phenyl and4-trifluoromethyl-phenyl.

Even more preferably Q¹ is phenyl, pyridyl, furanyl, thiophenyl,pyrazolyl or 1,2,3-thiadiazolyl, or phenyl, pyridyl, furanyl,thiophenyl, pyrazolyl or 1,2,3-thiadiazolyl substituted by one to threesubstituents independently selected from cyano, nitro, hydroxy, bromo,chloro, fluoro, methyl, trifluoromethyl, methoxy, methylthio,methylsulfinyl, methylsulfonyl or phenyl.

Yet even more preferably Q¹ is phenyl or pyridyl, or phenyl or pyridylsubstituted by one to two substituents independently selected fromcyano, hydroxy, chloro, fluoro, methyl, trifluoromethyl, methoxy,methylthio, methylsulfinyl, methylsulfonyl or phenyl.

Most preferably Q¹ is phenyl substituted by one or two substituentsselected from chloro, fluoro or methyl.

In one preferred embodiment Q¹ is 2-chloro-4-fluoro-phenyl.

In one preferred embodiment Q¹ is 3-chloro-2-fluoro-phenyl.

In one preferred embodiment Q¹ is 5-chloro-2-fluoro-phenyl.

In one preferred embodiment Q¹ is 3-chloro-2-methyl-phenyl.

In one preferred embodiment Q¹ is 2-chloro-phenyl.

In one preferred embodiment Q¹ is 3-chloro-phenyl.

In one preferred embodiment Q¹ is 4-cyano-phenyl.

In one preferred embodiment Q¹ is 2,5-dichloro-phenyl.

In one preferred embodiment Q¹ is 2,3-difluoro-phenyl.

In one preferred embodiment Q¹ is 2-fluoro-phenyl.

In one preferred embodiment Q¹ is 4-fluoro-phenyl.

In one preferred embodiment Q¹ is 2-methyl-phenyl.

A particularly preferred group of compounds are compounds of formula (Dwherein Q¹ is aryl or aryl substituted by one to five substituents R⁶,which may be the same or different.

Preferably Q¹ is phenyl or phenyl substituted by one to foursubstituents independently selected from cyano, nitro, hydroxy, bromo,chloro, fluoro, methyl, trifluoromethyl, methoxy, trifluoromethoxy,methylthio, methylsulfinyl, methylsulfonyl or phenyl.

More preferably Q¹ is phenyl or phenyl substituted by one to threesubstituents independently selected from cyano, nitro, hydroxy, bromo,chloro, fluoro, methyl, trifluoromethyl, methoxy, methylthio,methylsulfinyl, methylsulfonyl or phenyl.

Even more preferably Q¹ is phenyl or phenyl substituted by one to twosubstituents independently selected from cyano, hydroxy, chloro, fluoro,methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl,methylsulfonyl or phenyl.

Another particularly preferred group of compounds are compounds offormula (I) wherein Q¹ is heterocyclyl or heterocyclyl substituted byone to five substituents R⁶, which may be the same or different. Theheterocyclyl group is preferably a heteroaryl group.

Preferably Q¹ is pyridyl, furanyl, thiophenyl, pyrazolyl or1,2,3-thiadiazolyl, or pyridyl, furanyl, thiophenyl, pyrazolyl or1,2,3-thiadiazolyl substituted by one to four substituents independentlyselected from cyano, nitro, hydroxy, bromo, chloro, fluoro, methyl,trifluoromethyl, methoxy, trifluoromethoxy, methylthio, methylsulfinyl,methylsulfonyl or phenyl.

More preferably Q¹ is pyridyl, furanyl, thiophenyl, pyrazolyl or1,2,3-thiadiazolyl, or pyridyl, furanyl, thiophenyl, pyrazolyl or1,2,3-thiadiazolyl substituted by one to three substituentsindependently selected from cyano, nitro, hydroxy, bromo, chloro,fluoro, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl,methylsulfonyl or phenyl.

Even more preferably Q¹ is pyridyl or pyridyl substituted by one to twosubstituents independently selected from cyano, hydroxy, chloro, fluoro,methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl,methylsulfonyl or phenyl.

Most preferably Q¹ is pyridyl substituted by one to two substituentsindependently selected from chloro, fluoro or methyl.

Preferably each R⁶ is independently cyano, nitro, hydroxy, halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₄alkoxy-C₁-C₄-alkyl, C₃-C₆cycloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₄alkoxy-C₁-C₄-alkoxy, C₁-C₆alkylthio,C₁-C₆alkylsulfonyl, N,N-di-(C₁-C₆alkyl)amino,N,N-di-(C₁-C₆alkyl)aminocarbonyl, N,N-di-(C₁-C₆alkyl)aminosulfonyl,C₁-C₆alkylcarbonyl, C₁-C₆alkylcarbonyloxy, C₁-C₆alkoxycarbonyl orC₁-C₆alkylcarbonylamino.

More preferably each R⁶ is independently cyano, nitro, hydroxy, bromo,chloro, fluoro, iodo, methyl, ethyl, n-propyl, prop-2-yl, n-butyl,tert-butyl, chloromethyl, trifluoromethyl, methoxymethyl, cyclopropyl,methoxy, ethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,2-methoxy-ethoxy, methylthio, ethylthio, n-propylthio, n-butylthio,methylsulfonyl, prop-2-ylsulfonyl, N,N-dimethylamino,N,N-dimethylaminocarbonyl, N,N-dimethylaminosulfonyl, methylcarbonyl,methylcarbonyloxy, methoxycarbonyl, ethoxycarbonyl, methylcarbonylamino,aryl or aryl which is substituted by one to five substituentsindependently selected from cyano, nitro, hydroxy, chloro, fluoro,methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy, orheteroaryl or heteroaryl which is substituted by one to fivesubstituents independently selected from cyano, nitro, hydroxy, chloro,fluoro, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy.

Most preferably each R⁶ is independently cyano, nitro, chloro, fluoro,methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio,N,N-dimethylamino or methoxycarbonyl.

Preferably Q² is a moiety of formula (II).

Preferably Y¹ is cyano, halogen, methyl, ethyl, trifluoromethyl ormethoxymethyl.

More preferably Y¹ is cyano, bromo, chloro, methyl, ethyl,trifluoromethyl or methoxymethyl.

Even more preferably Y¹ is bromo, chloro, methyl, ethyl ormethoxymethyl.

Yet even more preferably Y¹ is bromo, methyl or ethyl.

Even more preferably Y¹ is methyl or ethyl.

Most preferably Y¹ is methyl.

Preferably Y² is hydrogen, chloro, fluoro or methyl.

Most preferably Y² is hydrogen.

Preferably Y³ is heptafluoropropyl, heptafluoroprop-2-yl,heptafluoropropylthio, heptafluoropropylsulfinyl,heptafluoropropylsulfonyl, heptafluoroprop-2-ylthio,heptafluoroprop-2-ylsulfinyl, heptafluoroprop-2-ylsulfonyl ornonafluorobut-2-yl.

In one embodiment Y³ is C₂-C₆ perfluoroalkyl, more preferably Y³ isheptafluoroprop-2-yl or nonafluorobut-2-yl.

In one embodiment Y³ is heptafluoroprop-2-yl.

In one embodiment Y³ is nonafluorobut-2-yl.

Preferably Y⁴ is hydrogen, chloro, fluoro or methyl.

Most preferably Y⁴ is hydrogen.

Preferably Y⁵ is cyano, halogen, methyl, ethyl or trifluoromethyl.

More preferably Y⁵ is cyano, bromo, chloro, methyl, ethyl ortrifluoromethyl.

Even more preferably Y⁵ is bromo, chloro, methyl or ethyl.

Yet even more preferably Y⁵ is bromo, methyl or ethyl.

Even more preferably Y⁵ is methyl or ethyl.

Most preferably Y⁵ is methyl.

Preferably Y⁶ is cyano, halogen, methyl, ethyl, trifluoromethyl ormethoxymethyl.

More preferably Y⁶ is cyano, bromo, chloro, methyl, ethyl,trifluoromethyl or methoxymethyl.

Even more preferably Y⁶ is bromo, chloro, methyl, ethyl ormethoxymethyl.

Yet even more preferably Y⁶ is bromo, methyl or ethyl.

Even more preferably Y⁶ is methyl or ethyl.

Most preferably Y⁶ is methyl.

Preferably Y⁷ is hydrogen, chloro, fluoro or methyl.

Most preferably Y⁷ is hydrogen.

Preferably Y⁸ is heptafluoropropyl, heptafluoroprop-2-yl,heptafluoropropylthio, heptafluoropropylsulfinyl,heptafluoropropylsulfonyl, heptafluoroprop-2-ylthio,heptafluoroprop-2-ylsulfinyl, heptafluoroprop-2-ylsulfonyl ornonafluorobut-2-yl.

In one embodiment Y⁸ is C₂-C₆ perfluoroalkyl, more preferably Y⁸ isheptafluoroprop-2-yl or nonafluorobut-2-yl.

In one embodiment Y⁸ is heptafluoroprop-2-yl.

In one embodiment Y⁸ is nonafluorobut-2-yl.

Preferably Y⁹ is cyano, halogen, methyl, ethyl, trifluoromethyl ormethoxymethyl.

More preferably Y⁹ is cyano, bromo, chloro, methyl, ethyl,trifluoromethyl or methoxymethyl.

Even more preferably Y⁹ is bromo, chloro, methyl, ethyl ormethoxymethyl.

Yet even more preferably Y⁹ is bromo, methyl or ethyl.

Even more preferably Y⁹ is methyl or ethyl.

Most preferably Y⁹ is methyl.

A preferred embodiment are compounds of formula (Ia) wherein A¹ is C—CN,and A², A³, A⁴ are CH.

A preferred embodiment are compounds of formula (Ib) wherein A² is C—CN,and A¹, A³, and A⁴ are CH.

A preferred embodiment are compounds of formula (Ic) wherein A³ is C—CN,and A¹, A², and A⁴ are CH.

A preferred embodiment are compounds of formula (Id) wherein A⁴ is C—CN,and A¹, A², and A³ are CH.

A preferred embodiment are compounds of formula (Ie) wherein A¹ is C—CN,A⁴ is C—F, and A² and A³ are CH.

A preferred embodiment are compounds of formula (If) wherein A¹ is C—CN,A² and A⁴ are C—F, and A³ is CH.

In a preferred embodiment Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2-methoxymethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2-bromo-6-methyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-diethyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-dichloro-4-(nonafluorobut-2-yl)-phenyl.

In a preferred embodiment Q² is2,6-dibromo-4-(nonafluorobut-2-yl)-phenyl.

In one embodiment of the invention R¹ and R² are independently of eachother hydrogen, C₁-C₄alkyl, or C₁-C₄alkylcarbonyl. The preferences forR¹ and R² are the same as set out for compounds of formula (I) exceptthat R¹ and R² cannot be allyl, propargyl, hydroxy, acetyloxy orbenzoyloxy.

In one embodiment of the invention each R³ is independently cyano,thiocyanato or N—C₁-C₄alkyl-aminothiocarbonyl. The preferences for R³are the same as set out for compounds of formula (I) except that R³cannot be aminothiocarbonyl.

In one embodiment of the invention each R⁵ is independently hydrogen,halogen, C₁-C₄alkyl or trifluoromethyl. The preferences for R⁵ are thesame as set out for compounds of formula (I) except that R⁵ cannot bemethoxy.

In one embodiment of the invention each R⁶ is independently cyano,nitro, hydroxy, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl, C₃-C₆cycloalkyl,C₃-C₆halocycloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, N—C₁-C₄alkylamino,N,N-di-(C₁-C₄alkyl)amino, C₁-C₄alkylcarbonyl, C₁-C₄alkylcarbonyloxy,C₁-C₄alkoxycarbonyl, C₁-C₄alkylcarbonylamino or phenyl. The preferencesfor R⁶ are the same as set out for compounds of formula (J).

In one embodiment of the invention Y¹ and Y⁵ are independently of eachother cyano, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl or C₁-C₃haloalkylsulfonyl. The preferences for Y¹ andY⁵ are the same as set out for compounds of formula (I) except that Y¹cannot be methoxymethyl.

In one embodiment of the invention Y⁶ and Y⁹ are independently of eachother cyano, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl or C₁-C₃haloalkylsulfonyl. The preferences for Y⁶ andY⁹ are the same as set out for compounds of formula (I) except that Y⁶and Y⁹ cannot be methoxymethyl.

Certain intermediates are novel and as such form a further aspect of theinvention.

One group of novel intermediates are compounds of formula (XIII)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in relation toformula I; or a salt or N-oxide thereof. The preferences for A¹, A², A³,A⁴, R², G² and Q² are the same as the preferences set out for thecorresponding substituents of the compounds of formula (I).

Another group of novel intermediates are compounds of formula (IX′)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in relation toformula I; or a salt or N-oxide thereof. The preferences for A¹, A², A³,A⁴, R², G² and Q² are the same as the preferences set out for thecorresponding substituents of the compounds of formula (I).

A further group of novel intermediates are compounds of formula (IX)

wherein A¹, A², A³, A⁴, R¹, R², G² and Q² are as defined in relation toformula I; or a salt or N-oxide thereof. The preferences for A¹, A², A³,A⁴, R¹, R², G² and Q² are the same as the preferences set out for thecorresponding substituents of the compounds of formula (I).

Another group of novel intermediates are compounds of formula (XI)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in relation toformula I and LG is a leaving group; or a salt or N-oxide thereof. Thepreferences for A¹, A², A³, A⁴, R², G² and Q² are the same as thepreferences set out for the corresponding substituents of the compoundsof formula (I). Preferably LG is halogen, more preferably fluoro orchloro, most preferably fluoro.

The compounds in Tables 1 to 63 below illustrate the compounds of theinvention.

Table 1:

Table 1 provides 38 compounds of formula (Ia) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in the table below.

Compound numbers Q¹ 1.01 5-bromo-furan-2-yl 1.02 2-bromo-phenyl 1.035-bromo-pyrid-3-yl 1.04 2-chloro-4-fluoro-phenyl 1.055-chloro-2-fluoro-phenyl 1.06 2-chloro-4-nitro-phenyl 1.072-chloro-5-nitro-phenyl 1.08 2-chloro-phenyl 1.09 3-chloro-phenyl 1.102-chloro-pyrid-3-yl 1.11 2-chloro-pyrid-4-yl 1.12 6-chloro-pyrid-3-yl1.13 5-chloro-thiophen-2-yl 1.14 3-chloro-5-trifluoromethyl-pyrid-2-yl1.15 4-cyano-phenyl 1.16 2,5-dichloro-phenyl 1.17 2,3-difluoro-phenyl1.18 1,3-dimethyl-1H-pyrazol-5-yl 1.19 2-fluoro-phenyl 1.204-fluoro-phenyl 1.21 2-fluoro-pyrid-3-yl 1.222-fluoro-3-trifluoromethyl-phenyl 1.23 2-fluoro-5-trifluoromethyl-phenyl1.24 4-fluoro-3-trifluoromethyl-phenyl 1.25 furan-2-yl 1.262-methoxy-phenyl 1.27 2-methyl-phenyl 1.28 3-methyl-pyrid-2-yl 1.294-methyl-1,2,3-thiadiazol-5-yl 1.30 2-methylthio-pyrid-3-yl 1.314-nitro-phenyl 1.32 phenyl 1.33 1,2,3-thiadiazol-4-yl 1.34 thiophen-2-yl1.35 2-trifluoromethoxy-phenyl 1.36 4-trifluoromethoxy-phenyl 1.372-trifluoromethyl-phenyl 1.38 4-trifluoromethyl-phenyl

Table 2:

Table 2 provides 38 compounds of formula (Ia) wherein Q² is2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 3:

Table 3 provides 38 compounds of formula (Ia) wherein Q² is2,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 4:

Table 4 provides 38 compounds of formula (Ia) wherein Q² is2-methoxymethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 5:

Table 5 provides 38 compounds of formula (Ia) wherein Q² is2-bromo-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 6:

Table 6 provides 38 compounds of formula (Ia) wherein Q² is2-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 7:

Table 7 provides 38 compounds of formula (Ia) wherein Q² is2,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 8:

Table 8 provides 38 compounds of formula (Ia) wherein Q² is2,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 9:

Table 9 provides 38 compounds of formula (Ia) wherein Q² is2,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 10:

Table 10 provides 38 compounds of formula (Ia) wherein Q² is2-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 11:

Table 11 provides 38 compounds of formula (Ia) wherein Q² is2,6-diethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 12:

Table 12 provides 38 compounds of formula (Ia) wherein Q² is2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 13:

Table 13 provides 38 compounds of formula (Ia) wherein Q² is2-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 14:

Table 14 provides 38 compounds of formula (Ia) wherein Q² is2-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 15:

Table 15 provides 38 compounds of formula (Ia) wherein Q² is2,6-dichloro-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 16:

Table 16 provides 38 compounds of formula (Ia) wherein Q² is2,6-dibromo-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 17:

Table 17 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in the table below.

Table 18:

Table 18 provides 38 compounds of formula (Ia′) wherein Q² is2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 19:

Table 19 provides 38 compounds of formula (Ia′) wherein Q² is2,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 20:

Table 20 provides 38 compounds of formula (Ia′) wherein Q² is2-methoxymethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 21:

Table 21 provides 38 compounds of formula (Ia′) wherein Q² is2-bromo-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 22:

Table 22 provides 38 compounds of formula (Ia′) wherein Q² is2-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 23:

Table 23 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 24:

Table 24 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 25:

Table 25 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 26:

Table 26 provides 38 compounds of formula (Ia′) wherein Q² is2-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 27:

Table 27 provides 38 compounds of formula (Ia′) wherein Q² is2,6-diethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 28:

Table 28 provides 38 compounds of formula (Ia′) wherein Q² is2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 29:

Table 29 provides 38 compounds of formula (Ia′) wherein Q² is2-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 30:

Table 30 provides 38 compounds of formula (Ia′) wherein Q² is2-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 31:

Table 31 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dichloro-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 32:

Table 32 provides 38 compounds of formula (Ia′) wherein Q² is2,6-dibromo-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 33:

Table 33 provides 38 compounds of formula (Ib) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 34:

Table 34 provides 38 compounds of formula (Ic) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 35:

Table 35 provides 38 compounds of formula (Id) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 36:

Table 36 provides 38 compounds of formula (Ie) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in the table below.

Table 37:

Table 37 provides 38 compounds of formula (Ie) wherein Q² is2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 38:

Table 38 provides 38 compounds of formula (Ie) wherein Q² is2,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 39:

Table 39 provides 38 compounds of formula (Ie) wherein Q² is2-methoxymethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 40:

Table 40 provides 38 compounds of formula (Ie) wherein Q² is2-bromo-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 41:

Table 41 provides 38 compounds of formula (Ie) wherein Q² is2-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 42:

Table 42 provides 38 compounds of formula (Ie) wherein Q² is2,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 43:

Table 43 provides 38 compounds of formula (Ie) wherein Q² is2,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 44:

Table 44 provides 38 compounds of formula (Ie) wherein Q² is2,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 45:

Table 45 provides 38 compounds of formula (Ie) wherein Q² is2-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 46:

Table 46 provides 38 compounds of formula (Ie) wherein Q² is2,6-diethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 47:

Table 47 provides 38 compounds of formula (Ie) wherein Q² is2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 48:

Table 48 provides 38 compounds of formula (Ie) wherein Q² is2-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 49:

Table 49 provides 38 compounds of formula (Ie) wherein Q² is2-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 50:

Table 50 provides 38 compounds of formula (Ie) wherein Q² is2,6-dichloro-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 51:

Table 51 provides 38 compounds of formula (Ie) wherein Q² is2,6-dibromo-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 52:

Table 52 provides 38 compounds of formula (If) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in the table below.

Table 53:

Table 53 provides 38 compounds of formula (If) wherein Q² is2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 54:

Table 54 provides 38 compounds of formula (If) wherein Q² is2,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 55:

Table 55 provides 38 compounds of formula (If) wherein Q² is2-methoxymethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 56:

Table 56 provides 38 compounds of formula (If) wherein Q² is2-bromo-6-methyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 57:

Table 57 provides 38 compounds of formula (If) wherein Q² is2-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 58:

Table 58 provides 38 compounds of formula (If) wherein Q² is2,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 59:

Table 59 provides 38 compounds of formula (If) wherein Q² is2,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 60:

Table 60 provides 38 compounds of formula (If) wherein Q² is2,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 61:

Table 61 provides 38 compounds of formula (If) wherein Q² is2-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 62:

Table 62 provides 38 compounds of formula (If) wherein Q² is2,6-diethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 63:

Table 63 provides 38 compounds of formula (If) wherein Q² is2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has thevalues listed in Table 1.

Table 64:

Table 64 provides 38 compounds of formula (If) wherein Q² is2-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 65:

Table 65 provides 38 compounds of formula (If) wherein Q² is2-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the valueslisted in Table 1.

Table 66:

Table 66 provides 38 compounds of formula (If) wherein Q² is2,6-dichloro-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 67:

Table 67 provides 38 compounds of formula (If) wherein Q² is2,6-dibromo-4-(nonafluorobut-2-yl)-phenyl and Q¹ has the values listedin Table 1.

Table 68:

Table 68 provides 16 compounds of formula (XIIIa) wherein Q² has thevalues listed in the table below.

Compound number Q² 68.01 2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl68.02 2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl 68.032,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl 68.042-methoxymethyl-6-methyl-4-(heptafluoroprop- 2-yl)-phenyl 68.052-bromo-6-methyl-4-(heptafluoroprop-2-yl)- phenyl 68.062-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl 68.072,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl 68.082,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl 68.092,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl 68.102-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl 68.112,6-diethyl-4-(nonafluorobut-2-yl)-phenyl 68.122-methoxymethyl-6-methyl-4-(nonafluorobut-2- yl)-phenyl 68.132-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl 68.142-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl 68.152,6-dichloro-4-(nonafluorobut-2-yl)-phenyl 68.162,6-dibromo-4-(nonafluorobut-2-yl)-phenyl

Table 69:

Table 69 provides 1 compound of formula (XIIIb) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 70:

Table 70 provides 1 compound of formula (XIIIc) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 71:

Table 71 provides 1 compound of formula (XIIId) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 72:

Table 72 provides 16 compounds of formula (XIIIe) wherein Q² has thevalues listed in Table 68.

Table 73:

Table 73 provides 16 compounds of formula (XIIIf) wherein Q² has thevalues listed in Table 68.

Table 74:

Table 74 provides 16 compounds of formula (IXa) wherein Q² has thevalues listed in the table below.

Compound number Q² 74.01 2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl74.02 2-ethyl-6-methyl-4-(heptafluoroprop-2-yl)-phenyl 74.032,6-diethyl-4-(heptafluoroprop-2-yl)-phenyl 74.042-methoxymethyl-6-methyl-4-(heptafluoroprop- 2-yl)-phenyl 74.052-bromo-6-methyl-4-(heptafluoroprop-2-yl)- phenyl 74.062-bromo-6-ethyl-4-(heptafluoroprop-2-yl)-phenyl 74.072,6-dichloro-4-(heptafluoroprop-2-yl)-phenyl 74.082,6-dibromo-4-(heptafluoroprop-2-yl)-phenyl 74.092,6-dimethyl-4-(nonafluorobut-2-yl)-phenyl 74.102-ethyl-6-methyl-4-(nonafluorobut-2-yl)-phenyl 74.112,6-diethyl-4-(nonafluorobut-2-yl)-phenyl 74.122-methoxymethyl-6-methyl-4-(nonafluorobut-2- yl)-phenyl 74.132-bromo-6-methyl-4-(nonafluorobut-2-yl)-phenyl 74.142-bromo-6-ethyl-4-(nonafluorobut-2-yl)-phenyl 74.152,6-dichloro-4-(nonafluorobut-2-yl)-phenyl 74.162,6-dibromo-4-(nonafluorobut-2-yl)-phenyl

Table 75:

Table 75 provides 1 compound of formula (IXb) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 76:

Table 76 provides 1 compound of formula (IXc) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 77:

Table 77 provides 1 compound of formula (IXd) wherein Q² is2,6-dimethyl-4-(heptafluoroprop-2-yl)-phenyl.

Table 78:

Table 78 provides 16 compounds of formula (IXe) wherein Q² has thevalues listed in Table 74.

Table 79:

Table 79 provides 16 compounds of formula (IXf) wherein Q² has thevalues listed in Table 74.

The compounds of the invention may be made by a variety of methods.

1) Compounds of formula (I), wherein G¹ and G² are oxygen, may be madeby treatment of compounds of formula (V), wherein G¹ is oxygen and R isOH, C₁-C₆alkoxy or Cl, F or Br with an amine of formula NHR²Q².

When R is OH such reactions are usually carried out in the presence of acoupling reagent, such as DCC (N,N′-dicyclohexylcarbodiimide), EDC(1-ethyl-3-[3-dimethylamino-propyl]carbodiimide hydrochloride) or BOP-Cl(bis(2-oxo-3-oxazolidinyl)phosphonic chloride), in the presence of abase, such as pyridine, triethylamine, 4-(dimethylamino)-pyridine ordiisopropylethylamine, and optionally in the presence of a nucleophiliccatalyst, such as hydroxybenzotriazole. When R is Cl, such reactions areusually carried out under basic conditions (for example in the presenceof pyridine, triethylamine, 4-(dimethylamino)-pyridine ordiisopropylethylamine), again optionally in the presence of anucleophilic catalyst. Alternatively, it is possible to conduct thereaction in a biphasic system comprising an organic solvent, preferablyethyl acetate, and an aqueous solvent, preferably a solution of sodiumhydrogen carbonate. When R is C₁-C₆alkoxy it is sometimes possible toconvert the ester directly to the amide by heating the ester and aminetogether in a thermal process.

2) Acid halides of formula (V), wherein G¹ is oxygen and R is Cl, F orBr, may be made from carboxylic acids of formula (V), wherein G¹ isoxygen and R is OH, under standard conditions, such as treatment withthionyl chloride or oxalyl chloride.

3) Carboxylic acids of formula (V), wherein G¹ is oxygen and R is OH,may be formed from esters of formula (V), wherein G¹ is oxygen and R isC₁-C₆alkoxy. It is known to a person skilled in the art that there aremany methods for the hydrolysis of such esters depending on the natureof the alkoxy group. One widely used method to achieve such atransformation is the treatment of the ester with an alkali hydroxide,such as sodium hydroxide, in a solvent, such as ethanol and/or water.

4) Esters of formula (V), wherein G¹ is oxygen and R is C₁-C₆alkoxy, maybe made by treatment of compounds of formula (IV), wherein R isC₁-C₆alkoxy, by acylation with a carboxylic acid of formula Q¹-COOH oran acid halide of formula Q¹-COHal, wherein Hal is Cl, F or Br, understandard conditions as described in 1).

5) Compounds of formula (IV), wherein R is C₁-C₆alkoxy, may be made fromcompounds of formula (VI) by sequential treatment with an alcohol R—OHunder acidic conditions and then formation of the N—R¹ bond. It is knownto a person skilled in the art that there are many reported methods forthe formation of this bond depending on the nature of the substituentR¹.

Alternatively, reactions based on oxidized versions of the alcohols suchas the corresponding aldehydes and ketones or based on more activatedanalogues of the alcohols such as the corresponding halides orsulfonates may be used. For example, reductive amination may be achievedby treatment of the amine with an aldehyde or ketone and a reducingagent such as sodium cyanoborohydride or sodium borohydride.Alternatively, alkylation may be achieved by treating the amine with analkylating agent such as an alkyl halide, optionally in the presence ofa base. Alternatively, arylation may be achieved by treatment of theamine with an aryl halide or sulfonate in the presence of a suitablecatalyst/ligand system, often a palladium (0) complex. Compounds offormula (VI) and alcohols of formula R—OH are either known compounds ormay be made by known methods known to a person skilled in the art.

6) Alternatively, compounds of formula (IV), wherein R is C₁-C₆alkoxy,may be made from a compound of formula (VII), wherein R is C₁-C₆alkoxyand LG is a leaving group, such as fluoro, chloro or sulfonate, vianucleophilic displacement of the leaving group by an amine of formulaR¹—NH₂.

Compounds of formula (VII) and amines of formula R¹—NH₂ are either knowncompounds or may be made by known methods known to a person skilled inthe art.

7) Compounds of formula (I), wherein G¹ and G² are sulfur, may be madefrom a compound of formula (I), wherein G¹ and G² are oxygen, bytreatment with a thio-transfer reagent, such as Lawesson's reagent orphosphorus pentasulfide.

8) Compounds of formula (I), wherein G¹ is sulfur and G² is oxygen, maybe made from compounds of formula (V), wherein G¹ is oxygen and R is OHor C₁-C₆alkoxy, by treatment with a thio-transfer reagent, such asLawessen's reagent or phosphorus pentasulfide, prior to coupling withthe amine of formula NHR²Q².

9) Alternatively, compounds of formula (I), wherein G¹ and G² areoxygen, may be made by the treatment of compounds of formula (IX),wherein G² is oxygen, with a carboxylic acid of formula Q¹-COOH or anacid halide of formula Q¹-COHal, wherein Hal is Cl, F or Br, understandard conditions as described in 1).

10) Compounds of formula (IX), wherein G² is oxygen, may be formed fromcompounds of formula (VIII), wherein P is a suitable protecting groupand R is OH, Cl or C₁-C₆alkoxy, by amide bond formation with an amine offormula NHR²Q² under standard conditions as described in 1), followed byremoval of the protecting group P under standard conditions.

11) Compounds of formula (VIII), wherein R is OH or C₁-C₆alkoxy, may bemade by the protection of the amine functionality in compounds offormula (IV), wherein R is OH or C₁-C₆alkoxy. Suitable protecting groupsinclude carbamates (such as tert-butyloxycarbonyl, allyloxycarbonyl andbenzyloxycarbonyl), trialkylsilyl groups (such astert-butyldimethylsilyl) and acyl groups (such as acetyl). The formationand removal of such groups is widely reported in the literature and isknown to a person skilled in the art.

12) For compounds of formula (VIII) and compounds of formula (IV), theesters (wherein R is C₁-C₆alkoxy) may be hydrolysed to the acids(wherein R is OH) by treatment with an alkali hydroxide, such as sodiumhydroxide, in a solvent, such as ethanol. The acids (wherein R is OH)may be converted to the acid chlorides (wherein R is Cl) by treatmentwith thionyl chloride or oxalyl chloride as described in 2) and 3).

13) Alternatively, it may be possible to convert compounds of formula(IV), wherein R is OH, Cl, F, Br or C₁-C₆alkoxy, directly to compoundsof formula (IX) by amide bond formation with an amine of formula NHR²Q²under standard conditions as described in 1).

14) Alternatively, compounds of formula (IX), wherein G² is oxygen, maybe made from compounds of formula (XI), wherein G² is oxygen and LG is aleaving group such as fluoro, chloro or sulfonate, by displacement ofthe leaving group with a compound of formula R¹—NH₂. Such reactions areusually performed under basic conditions.

15) Compounds of formula (XI) may be made from compounds of formula (X),wherein R is Cl or OH and LG is a leaving group as described in 14), viaamide bond formation under standard conditions as described in 1).Compounds of formula (X) and formula (IV) are either known compounds ormay be made by methods known to a person skilled in the art.

16) Compounds of formula (I), wherein G¹ is oxygen and G² is sulfur, maybe made by treatment of compounds of formula (XI), wherein G² is oxygenand LG is a leaving group, or compounds of formula (IX), wherein G² isoxygen, with a thio-transfer reagent such as Lawesson's reagent orphosphorus pentasulfide prior to elaborating to compounds of formula(I), wherein G¹ is oxygen and G² is sulfur, as described in 9).

17) Alternatively, compounds of formula (IX), wherein G² is oxygen, maybe prepared by formation of a N—R¹ bond in a compound of formula (IX′),wherein G² is oxygen, using the methods as described in 5).

18) Compounds of formula (IX′), wherein G² is oxygen, may be made by thereduction of a nitro compound of formula (XIII), wherein G² is oxygen.There are numerous methods for achieving such a transformation reportedin the literature such as treatment with tin chloride under acidicconditions, or hydrogenation catalysed by a noble metal such aspalladium on carbon.

19) Compounds of formula (XIII), wherein G² is oxygen, may be derivedfrom compounds of formula (XII), wherein R is OH, Cl, or C₁-C₆alkoxy,via acylation with an amine of formula NHR²Q² under the standardconditions as described in 1).

20) For compounds of formula (XII), the esters (wherein R isC₁-C₆alkoxy) may be hydrolysed to the acids (wherein R is OH) bytreatment with an alkali hydroxide, such as sodium hydroxide, in asolvent, such as ethanol as described in 3). The acids (wherein R is OH)may be converted to the acid chlorides (wherein R is Cl) by treatmentwith thionyl chloride or oxalyl chloride as described in 2). Compoundsof formula (XII) are either known or may be made by methods known to aperson skilled in the art.

21) Compounds of formula (XII) wherein R³ is cyano, can be made from acompound of formula (XII′) wherein LG is halogen, such as fluoride orchloride, by reaction with a cyanide salt, such as potassium cyanide,optionally in the presence of a base, such as potassium carbonate.

The displacement of a halogen with cyanide can also be carried out onintermediates of formula (XIII). In both instances the presence of thenitro group facilitates the displacement of the leaving group by thecyanide ion. Likewise compounds of formula (XII) and (XIII) wherein R³is thiocyanato, can be made from a compound of formula (XII′) or (XIII′)wherein LG is halogen, such as iodine, fluorine or chlorine, by reactionwith a thiocyanato salt, such as potassium thiocyanate or copperthiocyanate as described for example in Journal of the Chemical Society,Chemical Communications, (2), 8102; 1989 or Synthetic Communications,10(8), 633-6; 1980.

22) Compounds of formula (XII) wherein R³ is cyano, can be made from acompound of formula (XII′) wherein LG is an amine, by reaction with acyanide salt, such as copper cyanide, via a diazotisation reaction. Thedisplacement of an amine with cyanide can also be carried out onintermediates of formula (XIII).

23) Compounds of formula (I), wherein G¹ and G² are oxygen and R³ isaminothiocarbonyl, can be made, for example, by treatment of a compoundof formula (IV), (VI), (VII), (VIII), (X), (XII) wherein R³ is cyanowith P₄S₁₀ or H₂S as described, for example, in Journal of FluorineChemistry (2006), 127(1), 63-67, and Synthesis (2006), (2), 224-226 orSynthetic Communications (2003), 33(24), 4279-4284. Alternatively,compounds of formula (I), wherein G¹ and G² are oxygen and R³ isaminothiocarbonyl can be made, for example, by treatment of a compoundof formula (I), wherein R³ is cyano by reaction with sodium hydrogensulfide and magnesium chloride as described, for example, in SyntheticCommunications (2005), 35(5), 761-764.

24) Compounds of formula (I), wherein G¹ and G² are oxygen and R³ isN—C₁-C₄alkyl-aminothiocarbonyl can be made, for example, by treatment ofa compound of formula (I), wherein G¹ and G² are oxygen and R³ isaminothiocarbonyl by reaction with an N—C₁-C₄alkyl-amine, as described,for example, in U.S. Pat. No. 5,049,669 or Journal of Sulfur Chemistry(2006), 27(3), 203-212.

25) Compounds of formula (I), wherein G¹ and G² are oxygen and R³ isN,N-di-C₁-C₄alkyl-aminothiocarbonyl can be made, for example, bytreatment of a compound of formula (I), wherein G¹ and G² are oxygen andR³ is cyano by reaction with an N,N-di-C₁-C₄alkyl-amine in the presenceof sulfur, preferably with microwave irradiation, as described, forexample, in Synthetic Communications (2003), 33(24), 4279-4284.Alternatively, compounds of formula (I), wherein G¹ and G² are oxygenand R³ is N,N-di-C₁-C₄alkyl-aminothiocarbonyl can be made, for example,by treatment of a compound of formula (I), wherein G¹ and G² are oxygenand R³ is cyano by reaction with an N,N-di-C₁-C₄alkyl-dithiocarbamate asdescribed, for example, in Bulletin of the Chemical Society of Japan(1967), 40(9), 2209.

The compounds of formula (I) can be used to combat and controlinfestations of insect pests such as Lepidoptera, Diptera, Hemiptera,Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera,Hymenoptera and Isoptera and also other invertebrate pests, for example,acarine, nematode and mollusc pests. Insects, acarines, nematodes andmolluscs are hereinafter collectively referred to as pests. The pestswhich may be combated and controlled by the use of the inventioncompounds include those pests associated with agriculture (which termincludes the growing of crops for food and fibre products), horticultureand animal husbandry, companion animals, forestry and the storage ofproducts of vegetable origin (such as fruit, grain and timber); thosepests associated with the damage of man-made structures and thetransmission of diseases of man and animals; and also nuisance pests(such as flies).

Examples of pest species which may be controlled by the compounds offormula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid),Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids),Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper),Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips),Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis(boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (whiteflies), Bemisia tabaci (white fly), Ostrinia nubilalis (European cornborer), Spodoptera littoralis (cotton leafworm), Heliothis virescens(tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpazea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pierisbrassicae (white butterfly), Plutella xylostella (diamond back moth),Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustamigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulfureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans-(vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug).

The invention therefore provides a method of combating and controllinginsects, acarines, nematodes or molluscs which comprises applying aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I), or a composition containing acompound of formula (I), to a pest, a locus of pest, preferably a plant,or to a plant susceptible to attack by a pest, The compounds of formula(I) are preferably used against insects, acarines or nematodes.

The term “plant” as used herein includes seedlings, bushes and trees.

In order to apply a compound of formula (I) as an insecticide,acaricide, nematicide or molluscicide to a pest, a locus of pest, or toa plant susceptible to attack by a pest, a compound of formula (I) isusually formulated into a composition which includes, in addition to thecompound of formula (I), a suitable inert diluent or carrier and,optionally, a surface active agent (SFA). SFAs are chemicals which areable to modify the properties of an interface (for example,liquid/solid, liquid/air or liquid/liquid interfaces) by lowering theinterfacial tension and thereby leading to changes in other properties(for example dispersion, emulsification and wetting). It is preferredthat all compositions (both solid and liquid formulations) comprise, byweight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%,of a compound of formula (I). The composition is generally used for thecontrol of pests such that a compound of formula (I) is applied at arate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg perhectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at arate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

In another aspect the present invention provides an insecticidal,acaricidal, nematicidal or molluscicidal composition comprising aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I) and a suitable carrier or diluenttherefor. The composition is preferably an insecticidal, acaricidal,nematicidal or molluscicidal composition.

The compositions can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, fogging/smoke formulations, capsulesuspensions (CS) and seed treatment formulations. The formulation typechosen in any instance will depend upon the particular purpose envisagedand the physical, chemical and biological properties of the compound offormula (I).

Dustable powders (DP) may be prepared by mixing a compound of formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (I)with one or more water-soluble inorganic salts (such as sodium hydrogencarbonate, sodium carbonate or magnesium sulfate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of formula (I) and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound offormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulfates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of formula (J) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of formula (I) either as a liquid(if it is not a liquid at ambient temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound offormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in ECs or in EWs. An ME may be either an oil-in-wateror a water-in-oil system (which system is present may be determined byconductivity measurements) and may be suitable for mixing water-solubleand oil-soluble pesticides in the same formulation. An ME is suitablefor dilution into water, either remaining as a microemulsion or forminga conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound offormula (I). SCs may be prepared by ball or bead milling the solidcompound of formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitablepropellant (for example n-butane). A compound of formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with apyrotechnic mixture to form a composition suitable for generating, in anenclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound offormula (I) and they may be used for seed treatment. A compound offormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

A composition may include one or more additives to improve thebiological performance of the composition (for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of formula (I)).Such additives include surface active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SCand DC compositions described above. Compositions for treating seed mayinclude an agent for assisting the adhesion of the composition to theseed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surfaceSFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulfuric acid (for example sodium laurylsulfate), salts of sulfonated aromatic compounds (for example sodiumdodecylbenzenesulfonate, calcium dodecylbenzenesulfonate,butylnaphthalene sulfonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol ethersulfates (for example sodium laureth-3-sulfate), ether carboxylates (forexample sodium laureth-3-carboxylate), phosphate esters (products fromthe reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulfosuccinamates, paraffin or olefine sulfonates, taurates andlignosulfonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of formula (I) may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapour or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of formula (J) may also be injected into plants or sprayedonto vegetation using electrodynamic spraying techniques or other lowvolume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often requiredto withstand storage for prolonged periods and, after such storage, tobe capable of addition to water to form aqueous preparations whichremain homogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Such aqueous preparations may containvarying amounts of a compound of formula (I) (for example 0.0001 to 10%,by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilisers (forexample nitrogen-, potassium- or phosphorus-containing fertilisers).Suitable formulation types include granules of fertiliser. The mixturessuitably contain up to 25% by weight of the compound of formula (I).

The invention therefore also provides a fertiliser compositioncomprising a fertiliser and a compound of formula (I).

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula (I) may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may: provide a composition having a broader spectrum ofactivity or increased persistence at a locus; synergise the activity orcomplement the activity (for example by increasing the speed of effector overcoming repellency) of the compound of formula (I); or help toovercome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition. Examples of suitable pesticidesinclude the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,esfenvalerate, deltamethrin, cyhalothrin (in particularlambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin,fish safe pyrethroids (for example ethofenprox), natural pyrethrin,tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate;b) Organophosphates, such as, profenofos, sulprofos, acephate, methylparathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon,fenamiphos, monocrotophos, profenofos, triazophos, methamidophos,dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos,fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;c) Carbamates (including aryl carbamates), such as pirimicarb,triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,methomyl or oxamyl;d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,flufenoxuron or chlorfluazuron;e) Organic tin compounds, such as cyhexatin, fenbutatin oxide orazocyclotin;f) Pyrazoles, such as tebufenpyrad and fenpyroximate;g) Macrolides, such as avermectins or milbemycins, for exampleabamectin, emamectin benzoate, ivermectin, milbemycin, spinosad orazadirachtin;h) Hormones or pheromones;i) Organochlorine compounds such as endosulfan, benzene hexachloride,DDT, chlordane or dieldrin;j) Amidines, such as chlordimeform or amitraz;k) Fumigant agents, such as chloropicrin, dichloropropane, methylbromide or metam;l) Neonicotinoid compounds such as imidacloprid, thiacloprid,acetamiprid, nitenpyram, dinotefuran or thiamethoxam;m) Diacylhydrazines, such as tebufenozide, chromafenozide ormethoxyfenozide;n) Diphenyl ethers, such as diofenolan or pyriproxifen;

o) Indoxacarb; p) Chlorfenapyr; q) Pymetrozine; r) Spirotetramat,Spirodiclofen or Spiromesifen; or s) Flubendiamid or Rynaxypyr

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in thecomposition of the invention are(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetamide(SSF-129),4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide,α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916,cyamidazosulfamid),3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH-7281, zoxamide),N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide(MON65500),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole,azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S,bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazimchlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397,chinomethionate, chlorothalonil, chlorozolinate, clozylacon, coppercontaining compounds such as copper oxychloride, copper oxyquinolate,copper sulfate, copper tallate and Bordeaux mixture, cymoxanil,cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulfide1,1′-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb,difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-5-benzylthiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol,diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride,dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol,ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone (RPA407213), fenarimol,fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole,flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl,furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole,imazalil, imibenconazole, iminoctadine, iminoctadine triacetate,ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanylbutyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil,metalaxyl, metconazole, metiram, metiramn-zinc, metominostrobin,myclobutanil, neoasozin, nickel dimethyldithiocarbamate,nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds,oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin,pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-A1,phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D,polyram, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, propionic acid, pyrazophos, pyrifenox,pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155),sodium pentachlorophenate, spiroxamine, streptomycin, sulfur,tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl,thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole,validamycin A, vapam, vinclozolin, zineb and ziram.

The compounds of formula (I) may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™.

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

The following Examples illustrate, but do not limit, the invention.

PREPARATION EXAMPLES Example I1 Preparation of4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethylethyl)-phenyl]-3-nitro-benzamide

To a solution ofN-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-4-fluoro-3-nitro-benzamide(2.008 g, 4.4 mmol) (prepared according to WO 05/073165) inN,N-dimethylformamide (25 ml) was added sodium cyanide (0.237 g, 4.84mmol). The reaction mixture was stirred at ambient temperature for 48hours. Then water (20 ml) was added and the organic phase extractedthree times with ethyl acetate (3×100 ml). The combined organic extractswere washed with water and brine, dried over sodium sulfate andconcentrated. The residue was purified by column chromatography onsilica gel (eluent: cyclohexane/ethyl acetate 1:4) to give4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide(1.0 g, 49% yield). ¹H-NMR (400 MHz, CDCl₃): 8.85 (d, 1H), 8.38 (q, 1H),8.11 (d, 1H), 7.55 (s, 1H), 7.40 (s, 2H), 2.33 (s, 6H) ppm.

Analogous procedures were used to prepare the following compounds:

4-Cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.84 (s, 1H), 8.38 (q, 1H), 8.10 (d, 1H), 7.57(bs, 1H), 7.43 (s, 2H), 2.68 (q, 4H), 1.24 (t, 6H) ppm.

4-Cyano-N-[2-methoxymethyl-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide. ¹H-NMR (400 MHz, CDCl₃):9.18 (s, 1H), 8.88 (s, 1H), 8.39 (d, 1H), 8.11 (d, 1H), 7.55 (s, 2H),7.40 (s, 1H), 4.55 (s, 2H), 3.45 (s, 3H), 2.39 (s, 3H) ppm.

N-[2-Bromo-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-4-cyano-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.88 (s, 1H), 8.40 (d, 1H), 8.11 (d, 1H), 7.78(s, 2H), 7.52 (s, 11H), 2.44 (s, 3H) ppm.

N-[2-Bromo-6-ethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-4-cyano-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.87 (s, 1H), 8.39 (d, 1H), 8.10 (d, 1H), 7.80(s, 1H), 7.74 (s, 1H), 7.56 (s, 1H), 2.77 (q, 2H), 1.29 (t, 3H) ppm.

4-Cyano-N-[2,6-dibromo-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide.This was used in the next step without further purification.

4-Cyano-N-[2-ethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.86 (s, 1H), 8.39 (q, 1H), 8.10 (d, 1H), 7.80(s, 1H), 7.39 (s, 2H), 2.68 (q, 2H), 2.32 (s, 3H), 1.20 (t, 3H) ppm.

4-Cyano-N-[2,6-diethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.84 (s, 1H), 8.38 (q, 1H), 8.11 (d, 1H), 7.63(s, 1H), 7.26 (s, 2H), 2.67 (q, 4H), 1.23 (t, 6H) ppm.

N-[2-Bromo-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.90 (s, 1H), 8.40 (d, 1H), 8.10 (d, 1H), 7.92(s, 1H), 7.74 (s, 1H), 7.51 (s, 1H), 2.43 (s, 3H) ppm.

N-[2-Bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.89 (s, 1H), 8.40 (d, 1H), 8.10 (d, 1H), 7.82(s, 1H), 7.78 (s, 1H), 7.55 (s, 1H), 2.75 (q, 2H), 1.26 (t, 3H) ppm.

2-Cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-5-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.81 (m, 1. H), 8.69 (m, 1H), 8.33 (d, 1H),7.49 (s, 2H), 2.21 (s, 6H) ppm.

2-Cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide.¹H-NMR (400 MHz, CDCl₃): 10.67 (s, 1H), 8.58 (d, 1H), 8.40 (d, 1H), 8.02(t, 1H), 7.49 (s, 2H), 2.53 (q, 4H), 1.17 (t, 6H) ppm.

Example I2 Preparation of3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide

4-Cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide(1.0 g, 2.16 mmol) (Example I1) was dissolved in diethylene glycoldimethyl ether (“diglyme”) (25 ml) and tin chloride (1.229 g, 6.48 mmol)was added. The mixture was cooled to 0° C. and aqueous hydrochloric acid(concentrated) (4 ml) was added slowly. The reaction mixture was stirredat 80° C. for 0.5 hours. Aqueous sodium hydroxide (30% w/v) (80 ml) wasadded to adjust the pH to 7-8. The aqueous phase was extracted threetimes with ethyl acetate (200 ml). The combined organic extracts weredried over sodium sulfate and concentrated. The residue was purified bycolumn chromatography on silica gel (eluent: cyclohexane/ethyl acetate1:1 to 0:1) to give3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(0.48 g, 51% yield). ¹H-NMR (400 MHz, CDCl₃): 7.54 (s, 1H), 7.49 (d,2H), 7.36 (m, 3H), 7.15 (q, 1H), 2.3 (s, 6H) ppm.

Analogous procedures or well known procedures such as hydrogenation inthe presence of a palladium catalyst, as described in, for example,Journal of Medicinal Chemistry (2005), 48(24), 7560 or Journal ofMedicinal Chemistry (2005), 48(6), 1729, and reduction with sodiumhydrogen sulfite in a biphasic system with tetrabutylammonium bromide asphase transfer catalyst (see Example I3) as described in, for example,Journal of Medicinal Chemistry (2006), 49(3), 955-970, were used toprepare the following compounds:

3-Amino-4-cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.53 (d, 1H), 7.40 (s, 2H), 7.33 (m, 2H), 4.65(bs, 2H), 2.67 (q, 4H), 1.19 (t, 6H) ppm.

3-Amino-4-cyano-N-[2-methoxymethyl-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.78 (s, 1H), 7.53 (m, 2H), 7.38 (s, 1H), 7.18(d, 1H), 4.65 (s, 2H), 4.49 (s, 2H), 3.40 (s, 3H), 2.38 (s, 3H) ppm.

3-Amino-N-[2-bromo-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-4-cyano-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.72 (s, 1H), 7.60 (s, 1H), 7.54 (d, 1H), 7.50(s, 1H), 7.35 (s, 1H), 7.21 (d, 1H), 4.65 (s, 2H), 2.40 (s, 3H) ppm.

3-Amino-N-[2-bromo-6-ethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-4-cyano-benzamide.¹H-NMR (400 MHz, acetone d⁶): 7.70 (s, 1H), 7.54 (s, 1H), 7.46 (d, 1H),7.39 (s, 1H), 7.18 (d, 1H), 5.70 (s, 2H), 2.70 (q, 2H), 1.10 (t, 3H)ppm.

3-Amino-4-cyano-N-[2,6-dibromo-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.88 (s, 2H), 7.63 (s, 1H), 7.54 (d, 1H), 7.35(s, 1H), 7.21 (d, 1H), 4.67 (bs, 2H) ppm.

3-Amino-4-cyano-N-[2-ethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.53 (d, 1H), 7.33 (m, 4H), 7.15 (q, 1H), 4.64(bs, 2H), 2.67 (q, 2H), 2.33 (s, 3H), 1.21 (t, 3H) ppm.

3-Amino-4-cyano-N-[2,6-diethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.74 (d, 1H), 7.38 (s, 2H), 7.34 (m, 2H), 7.15(q, 1H), 4.66 (bs, 2H), 2.66 (q, 4H), 1.21 (t, 6H) ppm.

3-Amino-N-[2-bromo-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.71 (s, 1H), 7.60 (s, 1H), 7.53 (d, 1H), 7.48(s, 1H), 7.35 (s, 1H), 7.21 (d, 1H), 4.65 (s, 2H), 2.41 (s, 3H) ppm.

3-Amino-N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamide.¹H-NMR (400 MHz, acetone d⁶): 7.70 (s, 1H), 7.53 (s, 1H), 7.44 (d, 1H),7.40 (s, 1H), 7.19 (d, 1H), 5.70 (s, 2H), 2.70 (q, 2H), 1.08 (t, 3H)ppm.

5-Amino-2-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.7 (s, 1H), 7.43 (s, 2H), 7.14 (d, 1H), 7.98(m, 1H), 4.3 (s, 2H), 2.2 (s, 6H) ppm.

3-Amino-2-cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 7.5-7.44 (m, 4H), 7.28 (s, 1H), 6.94 (d, 1H),5.60 (s, 2H), 2.50 (q, 4H), 1.13 (t, 6H) ppm.

Example I3 Alternative preparation of3-amino-N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamide

N-[2-Bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamide(63.9 g, 102.6 mmol) was dissolved in tetrahydrofuran (1200 ml). Aqueoussodium hydroxide (0.1 M, 550 ml), sodium hydrogen sulfite (65.3 g, 307.7mmol) and tetrabutylammonium bromide (“TBAB”) (3.4 g, 10.3 mmol) wereadded. The mixture was vigorously stirred at 65° C. Further portions ofsodium hydrogen sulfite were added after 20 minutes (65.3 g, 307.7 mmol)and after 80 minutes (32.7 g, 153.8 mmol). The reaction mixture wasstirred at 65° C. for 30 minutes. Then the reaction mixture was cooledto 25° C. and diluted with ethyl acetate (1300 ml). The phases wereseparated and the organic phase was extracted with ethyl acetate (300ml). The combined organic phases were washed with water, aqueous sodiumhydrogen carbonate (10% w/v) (400 ml) and brine, dried over sodiumsulfate and concentrated to yield3-amino-N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamideas a yellow solid (63.1 g) which was used in the next step withoutfurther purification.

Example I4 Preparation of4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-methylamino-benzamide

3-Amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(3.01 g, 6.95 mmol) (Example I2) was dissolved in acetonitrile (50 ml)and aqueous formaldehyde (36.5% w/v) (0.64 ml, 6.95 mmol) and aceticacid (30 ml) were added successively. The reaction mixture was stirredat ambient temperature for 45 minutes. Then sodium borohydride (0.44 g,6.95 mmol) and more acetic acid (5 ml) were added. The reaction mixturewas stirred at ambient temperature for 2 hours. The reaction mixture wasconcentrated. The residue was dissolved in ethyl acetate and thesolution washed with aqueous sodium hydroxide (1N). The aqueous phasewas extracted three times with ethyl acetate (200 ml). The combinedorganic extracts were dried over sodium sulfate and concentrated. Theresidue was purified by column chromatography on silica gel (eluent:cyclohexane/ethyl acetate 1:5) to give4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-methylamino-benzamide(1.80 g, 58% yield). M.p. 204-206° C. ¹H-NMR (400 MHz, CDCl₃): 7.53 (d,1H), 7.37 (s, 3H), 7.23 (s, 1H), 7.10 (q, 1H), 5.88 (d, 1H), 3.02 (d,3H), 2.35 (s, 6H) ppm.

An analogous procedure was used to prepare the following compound:

4-Cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-methylamino-benzamide.M.p. 199-202° C. ¹H-NMR (400 MHz, CDCl₃): 7.53 (d, 1H), 7.40 (s, 2H),7.31 (s, 1H), 7.23 (s, 1H), 7.08 (q, 1H), 5.88 (d, 1H), 3.02 (d, 3H),2.69 (q, 4H), 1.24 (t, 6H) ppm.

The general method as described in Example P2 was then used to prepare anumber of compounds (Compound No. C1 to C40 of Table C) in parallel.

An analogous procedure was used to prepare the following compound:

4-Cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-ethylamino-benzamideusing acetaldehyde as reagent. ¹H-NMR (400 MHz, CDCl₃): 7.52 (d, 1H),7.37 (s, 2H), 7.35 (s, 1H), 7.23 (s, 1H), 7.08 (m, 1H), 4.69 (t, 1H),3.35 (m, 2H), 2.35 (s, 6H), 1.24 (t, 3H) ppm.

Example I5 Preparation of 3-cyano-5-nitro-benzoic acid

Solution 1: 3-Amino-5-nitro-benzoic acid (10 g, 54.9 mmol) was dissolvedin aqueous hydrochloric acid (concentrated) (55 ml) and diluted withwater (200 ml). A solution of sodium nitrite (3.788 g, 54.90 mmol) inwater (30 ml) was added at 0-5° C.

Solution 2: To a solution of copper sulfate hydrate (28.786 g, 115.29mmol) in water (120 ml) was added a solution of potassium cyanide(27.528 g, 422.73 mmol) in water (30 ml).

Solution 2 was heated to 65° C. The pH of Solution 1 was adjusted to 6-7with aqueous sodium carbonate (saturated) at 0-5° C. Solution 1 wasadded dropwise to Solution 2 at 65° C. The reaction mixture was heatedto reflux for 40 minutes. The reaction mixture was allowed to cool toambient temperature and acidified with aqueous hydrochloric acid (2N).The aqueous phase was extracted three times with ethyl acetate (3×200ml). The combined organic extracts were washed with aqueous sodiumphosphite (saturated), water, brine and concentrated to give3-cyano-5-nitro-benzoic acid (7.2 g, 68% yield) which was used withoutfurther purification. ¹H-NMR (400 MHz, DMSO-d₆): 9.0 (s, 1H), 8.82 (s,1H), 8.70 (s, 1H) ppm.

Similarly, 4-cyano-3-nitro-benzoic acid was prepared from4-amino-3-nitro-benzoic acid. ¹H-NMR (400 MHz, DMSO-d₆): 8.79 (s, 1H),8.40 (d, 1H), 8.31 (d, 1H) ppm.

Example I6 Alternative preparation of 4-cyano-3-nitro-benzoic acid

4-Hydroxy-3-nitro-benzoic acid methyl ester (55.9 g, 283 mmol) andpyridine (67 g, 849 mmol) were dissolved in dichloromethane (1100 ml).The yellow mixture was cooled to 0° C. and trifluoromethane sulfonicanhydride (87.8 g, 311 mmol) was added dropwise within 60 minutes at 0°C.-5° C. After 90 minutes at 5° C. the reaction mixture was washed withaqueous hydrochloric acid (2M), then with aqueous sodium hydrogencarbonate (10% w/v) and finally with brine. The organic phase was driedover sodium sulfate and concentrated to yield3-nitro-4-trifluoromethanesulfonyloxy-benzoic acid methyl ester (89.7 g)as a yellow oil which was used in the next step without furtherpurification. ¹H-NMR (400 MHz, CDCl₃): 8.80 (s, 1H), 8.40 (d, 1H), 7.58(d, 1H), 4.00 (s, 3H) ppm.

3-Nitro-4-trifluoromethanesulfonyloxy-benzoic acid methyl ester (89.7 g,272 mmol), zinc cyanide (19.2 g, 163 mmol) andtetrakis(triphenylphosphine)palladium(0) (15 g) were suspended inN,N-dimethylformamide (2500 ml). The reaction mixture was stirred for 3hours at 100° C. under an inert atmosphere. The solvent was evaporatedand the residue was purified by column chromatography on silica gel(eluent: cyclohexane/ethyl acetate 3:1) to give 4-cyano-3-nitro-benzoicacid methyl ester (34.0 g, 60.7% yield). ¹H-NMR (400 MHz, CDCl₃): 8.92(s, 1H), 8.48 (d, 1H), 8.04 (d, 1H), 4.03 (s, 3H) ppm.

4-Cyano-3-nitro-benzoic acid methyl ester (13.4 g, 61.6 mmol) wasdissolved in tetrahydrofuran (74 ml) and aqueous sodium hydroxide (1M)(73.9 ml) was added. The reaction mixture was stirred at 25° C. for 4hours. Then the reaction mixture was diluted with water (700 ml) andacidified with aqueous hydrochloric acid (1M). The mixture was extractedwith ethyl acetate. The combined organic phases were dried over sodiumsulfate and concentrated. 4-Cyano-3-nitro-benzoic acid (12.0 g) was usedin the next step without further purification. ¹H-NMR (400 MHz,DMSO-d⁶): 13.00 (bs, 1H), 8.79 (s, 1H), 8.40 (d, 1H), 8.30 (d, 1H) ppm.

Example I7 Alternative preparation of 4-cyano-3-nitro-benzoic acid

Under an inert atmosphere, periodic acid (492 g, 2.17 mol) was dissolvedin acetonitrile (7.7 l) with vigorous stirring, and then, after 15minutes chromium(VI) oxide (25 g, 0.25 mol) and4-methyl-2-nitro-benzonitrile (100 g, 0.62 mol) were added successively.The reaction mixture was stirred at ambient temperature for 16 hours.The reaction mixture was decanted and the supernatant filtered. Thefiltrate was concentrated and the residue partitioned between aqueoussodium carbonate (1M) and dichloromethane. The precipitate was isolatedby filtration to give 4-cyano-3-nitro-benzoic acid (150 g). The filtratewas extracted twice with dichloromethane and was then acidified byaddition of aqueous hydrochloric acid (4N) to pH 1. The acidifiedfiltrate was then extracted three times with dichloromethane. Thecombined organic extracts were dried over sodium sulfate andconcentrated. This residue was partitioned between aqueous sodiumcarbonate (1M) and dichloromethane. The precipitate was isolated byfiltration to give 4-cyano-3-nitro-benzoic acid (26.67 g). Total yield:150 g+26.67 g=176.67 g; 74.5% yield.

Example I8 Preparation of3-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-5-nitro-benzamide

To a suspension of 3-cyano-5-nitro-benzoic acid (7.2 g, 37.5 mmol)(Example I5) in dichloromethane (40 ml) was added oxalyl chloride (3.808ml, 45 mmol) at ambient temperature, followed by N,N-dimethylformamide(0.2 ml). The reaction mixture was stirred for 1 hour at ambienttemperature and then heated to reflux for 3 hours. The reaction mixturewas allowed to cool to ambient temperature and then concentrated. Theresidue was suspended in tetrahydrofuran (50 ml).2,6-Dimethyl-4-(heptafluoroprop-2-yl)aniline (9.761 g, 33.7 mmol)(prepared according to EP 1,006,102) was dissolved in tetrahydrofuran(50 ml) and pyridine (6.035 ml, 75 mmol) was added. The mixture wascooled to 0° C. and the solution of 2-fluoro-5-nitro-benzoyl chloridewas added. The reaction mixture was stirred at ambient temperature for12 hours. Then aqueous sodium hydrogen carbonate (saturated) (100 ml)was added and the organic phase extracted twice with ethyl acetate(2×200 ml). The combined organic extracts were dried over sodium sulfateand concentrated. The residue was purified by column chromatography onsilica gel (eluent: cyclohexane/ethyl acetate 6:1) to give3-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-5-nitro-benzamide(12 g, 77% yield). ¹H-NMR (400 MHz, CDCl₃): 8.99 (m, 1H), 8.72 (m, 1H),8.6 (m, 1H), 7.80 (s, 1H), 7.4 (s, 2H), 2.33 (s, 6H) ppm.

Similarly, as an alternative synthesis,N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamidewas prepared from 4-cyano-3-nitro-benzoic acid (Example I5, 16 or 17).

Example I9 Preparation of5-amino-3-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide

3-Cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-5-nitro-benzamide(12.0 g, 25.9 mmol) (Example I8) was dissolved in isopropanol (200 ml)and tin chloride (14.73 g, 77.7 mmol) was added. The mixture was cooledto 0° C. and aqueous hydrochloric acid (concentrated) (30 ml) was addedslowly. The reaction mixture was stirred at 80° C. for 0.5 hours. 1/3 ofthe total volume of isopropanol was evaporated. Water (100 ml) was addedto the concentrated mixture and aqueous sodium hydroxide (4N) was addedto adjust the pH to 7-8. The aqueous phase was extracted three timeswith ethyl acetate (3×200 ml). The combined organic extracts were driedover sodium sulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: cyclohexane/ethyl acetate 4:1 to0:1) to give5-amino-3-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(10.6 g, 94.4% yield). ¹H-NMR (400 MHz, CDCl₃): 7.47 (s, 1H), 7.44 (s,2H), 7.36 (s, 2H), 7.07 (s, 1H), 4.11 (bs, 2H), 2.32 (s, 6H) ppm.

Example I10 Preparation of 4-cyano-2,3-difluoro-benzoic acid

A solution of periodic acid (4.787 g, 21 mmol) in acetonitrile (75 ml)under a nitrogen atmosphere was stirred at ambient temperature for 15minutes before the addition of chromium(VI) oxide (120 mg, 1.2 mmol) and2,3-difluoro-4-methyl-benzonitrile (0.919 g, 6 mmol). The reactionmixture was stirred for one hour at ambient temperature. The reactionmixture was filtered and the filtrate concentrated. The residue wastaken up into aqueous sodium carbonate (1M) and washed twice withdichloromethane. The aqueous phase was acidified with aqueoushydrochloric acid (4M) and extracted three times with dichloromethane.The combined organic phases were dried over sodium sulfate andconcentrated to give 4-cyano-2,3-difluoro-benzoic acid (0.77 g, 70%yield) which was used without further purification.

Example I11 Preparation of4-cyano-2,3-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide

To a solution of 4-cyano-2,3-difluoro-benzoic acid (623 mg, 3.4 mmol)(Example I10) and N,N-dimethylformamide (2 drops) in dichloromethane (17ml) under a nitrogen atmosphere was added oxalyl chloride (0.3455 ml,4.08 mmol). The reaction mixture was stirred for one hour at ambienttemperature and then at 60° C. for 1.5 hours. The reaction mixture wasconcentrated and the residue dissolved in tetrahydrofuran (5 ml). Thesolution was added drop-wise to a solution of2,6-dimethyl-4-(heptafluoroprop-2-yl)aniline (prepared according to EP1,006,102) (787 mg, 2.72 mmol) and pyridine (547 μl, 6.8 mmol) intetrahydrofuran (12 ml). The reaction mixture was stirred at ambienttemperature for 16 hours. Then the reaction mixture was poured intoaqueous sodium hydrogen carbonate (1M) and the mixture extracted threetimes with ethyl acetate. The combined organic phases were dried oversodium sulfate and concentrated. The residue was purified byreverse-phase chromatography (eluent: trifluoroaceticacid/water/acetonitrile 1:4:5 to 1:1:8) to give4-cyano-2,3-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(0.675 g, 44% yield). ¹H-NMR (400 MHz, CDCl₃): 2.35 (6H, s), 7.38 (2H,s), 7.57 (1H, m), 7.79 (1H, d), 8.03 (1H, m) ppm.

Similarly,N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-fluoro-benzamidewas prepared from 4-cyano-3-fluoro-benzoic acid (commerciallyavailable). ¹H-NMR (400 MHz, CDCl₃): 7.81 (m, 3H), 7.76 (s, 1H), 7.63(s, 1H), 7.52 (s, 1H), 2.75 (q, 2H), 1.23 (t, 3H) ppm.

Similarly,4-cyano-3-fluoro-N-[2-methoxymethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamidewas from 4-cyano-3-fluoro-benzoic acid (commercially available). ¹H-NMR(400 MHz, CDCl₃): 8.95 (s, 1H), 7.82 (m, 2H), 7.53 (s, 1H), 7.36 (s,1H), 4.5 (s, 2H), 3.39 (s, 3H), 2.37 (s, 3H) ppm.

Example I12 Preparation of3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,22-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide

To a solution of4-cyano-2,3-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(0.693 g, 1.53 mmol) (Example I11) in dimethyl-sulfoxide (2.32 ml) wasadded ammonium carbonate (69 mg, 1.75 mmol). The reaction mixture washeated to 100° C. for 16 hours. The reaction mixture was allowed to coolto ambient temperature and then partitioned between water and ethylacetate. The organic phase was dried over sodium sulfate andconcentrated. The residue was purified by column chromatography onsilica gel (eluent: cyclohexane/ethyl acetate 7:3) to give3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluorobenzamide(290 mg, 42% yield). ¹H-NMR (400 MHz, CDCl₃): 2.35 (6H, s), 4.68 (1H,bs), 7.35-7.41 (4H, m), 7.74 (1H, d) ppm.

Analogous procedures were used to prepare the following compounds:

3-Amino-4-cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.73 (1H, d), 7.42-7.32 (4H, m), 4.7 (2H, s),4.70 (2H, s), 2.70 (4H, q), 1.23 (6H, t) ppm.

3-Amino-4-cyano-2-fluoro-N-[2-methoxymethyl-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 8.82 (1H, d), 7.52 (1H, s), 7.43-7.32 (3H, m),4.7 (2H, s), 4.5 (2H, s), 3.40 (3H, s), 2.37 (3H, s) ppm.

Similarly, as an alternative synthesis,3-amino-N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamidewas prepared fromN-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-fluoro-benzamide(Example I1).

Example I13 Preparation of3-amino-4-cyano-N-[2-methoxymethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamide

Ammonia gas was added for 30 minutes to a solution of4-cyano-3-fluoro-N-[2-methoxymethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamide(0.981 g, 1.90 mmol) (Example I1) in dimethylsulfoxide (20 ml). Thereaction mixture was heated to 100° C. for 16 hours. The reactionmixture was allowed to cool to ambient temperature and more ammonia gaswas added. The reaction mixture was heated to 100° C. for a further 16hours. The reaction mixture was allowed to cool to ambient temperatureand then partitioned between water and ethyl acetate. The aqueous phasewas extracted 3 times with ethyl acetate. The combined organic phaseswere dried over sodium sulfate and concentrated. The residue waspurified by column chromatography on silica gel (eluent:cyclohexane/ethyl acetate 3:1) to give3-amino-4-cyano-N-[2-methoxymethyl-6-methyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-benzamide(640 mg, 66% yield). ¹H-NMR (400 MHz, CDCl₃): 8.77 (s, 1H), 7.51 (m,2H), 7.37 (m, 2H), 7.18 (d, 1H), 4.63 (s, 2H), 4.49 (s, 2H), 3.37 (s,3H), 2.36 (s, 3H) ppm.

Example I14 Preparation of3-amino-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2,4,5-trifluoro-benzamide

3-Amino-2,4,5-trifluoro-benzoic acid (commerically available) (12.5 g,65.50 mmol) was heated with thionyl chloride (110 ml) at 90° C. for 2hours under a nitrogen atmosphere. The excess thionyl chloride wasremoved in vacuo. To a solution of the residue (13.37 g, 52.30 mmol) indichloromethane (218 ml) under a nitrogen atmosphere was added asolution of 2,6-dimethyl-4-(heptafluoroprop-2-yl)aniline (preparedaccording to EP 1,006,102) (15.12 g, 52.30 mmol) in pyridine (4.2 ml,52.30 mmol). The reaction mixture was stirred at ambient temperature for2 hours and then extracted with aqueous hydrochloric acid (1M). Theaqueous phase was extracted twice with dichloromethane. The combinedorganic phases were washed with aqueous sodium hydrogen carbonate (1M),dried over sodium sulfate and concentrated. The residue was purified bycolumn chromatography on silica gel (eluent: cyclohexane/ethyl acetate7:3) to give3-amino-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2,4,5-trifluoro-benzamide(18.4 g, 76% yield). ¹H-NMR (400 MHz, CDCl₃): 2.35 (6H, s), 4.07 (2H,bs), 7.3-7.35 (1H, m), 7.36 (2H, s), 7.83 (1H, d) ppm.

Example I15 Preparation ofN-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-2,4,5-trifluoro-benzamide

To a solution of3-amino-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2,4,5-trifluoro-benzamide(32.8 g, 71 mmol) (Example I14) and trifluoro-acetic acid (237 ml) inchloroform (118 ml) was added drop-wise aqueous hydrogen peroxide (67ml) (35% w/v). The reaction mixture was kept at approximately 50° C.with external cooling. The reaction mixture was stirred at 55° C. for 30minutes, then poured onto a mixture of ice and water. The mixture wasextracted twice with dichloromethane. The combined organic phases werewashed with aqueous sodium hydrogen carbonate (1M), dried over sodiumsulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: cyclohexane/ethyl acetate 7:3) togiveN-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-2,4,5-trifluoro-benzamide(23.94 g, 68.5% yield). ¹H-NMR (400 MHz, CDCl₃): 2.35 (6H, s), 7.38 (2H,s), 7.68 (1H, d), 8.25 (1H, m) ppm.

Example I16 Preparation of4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide

To a solution ofN-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-2,4,5-trifluoro-benzamide(6.77 g, 13.75 mmol) (Example I15) in N,N-dimethylformamide (137 ml) at0° C. was added sodium cyanide (740 mg, 15.13 mmol). The reactionmixture was stirred at 0° C. for one hour and then at ambienttemperature for 16 hours. The reaction mixture was concentrated and theresidue partitioned between water and dichloromethane. The combinedorganic phases were dried over sodium sulfate and concentrated. Theresidue was purified by column chromatography on silica gel (eluent:cyclohexane/ethyl acetate 8:2) to give4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide(3.2 g, 46.6% yield). ¹H-NMR (400 MHz, CDCl₃): 2.35 (6H, s), 7.38 (2H,s), 7.83 (1H, d), 8.29 (1H, m) ppm.

Example I17 Preparation of3-amino-4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide

A solution of4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide(5.99 g, 12 mmol) (Example I16) in methanol was reacted with hydrogenfor 16 hours in the presence of 10% palladium on carbon (40 bar, 40°C.). The reaction mixture was filtered to remove the catalyst and thefiltrate concentrated. The residue was purified by column chromatographyon silica gel (eluent: cyclohexane/ethyl acetate 7:3) to give3-amino-4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(0.953 g, 17% yield). ¹H-NMR (400 MHz, CDCl₃): 2.36 (6H, s), 4.82 (2H,bs), 7.12 (1H, m), 7.38 (2H, s), 7.78 (1H, d) ppm.

Analogous procedures were used to prepare the following compounds:

3-Amino-4-cyano-N-[2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2,5-difluoro-benzamide.¹H-NMR (400 MHz, CDCl₃): 1.22 (6H, t), 2.68 (4H, q), 4.85 (2H, s), 7.12(1H, m), 7.41 (2H, s), 7.77 (1H, d) ppm.

3-Amino-4-cyano-2,5-difluoro-N-[2-methoxymethyl-6-methyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide.¹H-NMR (400 MHz, CDCl₃): 2.35 (3H, s), 3.41 (3H, s), 4.49 (2H, s), 4.84(2H, s), 7.12 (1H, m), 7.41 (1H, s), 7.52 (1H, s), 8.89 (1H, d) ppm.

Example P1 Preparation of4-cyano-3-(4′-cyano-benzoylamino)-N-[2,6-dimethyl-4-(1,2,22-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Compound No. A1 of Table A)

3-Amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(65 mg, 0.15 mmol) (Example I2) was dissolved in a biphasic mixture ofethyl acetate (3 ml) and aqueous sodium hydrogen carbonate (1N) (3 ml).4-Cyano-benzoyl chloride (50 mg, 0.30 mmol) was added under vigorousstirring. The reaction mixture was stirred for 3 hours at ambienttemperature. The phases were separated. The organic phase was dried oversodium sulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: cyclohexane/ethyl acetate 2:1) togive Compound No. A1 of Table A (81.5 mg, 97% yield). ¹H-NMR (400 MHz,CHCl₃): 9.15 (s, 1H), 8.5 (s, 1H), 8.05 (m, 2H), 7.88 (m, 4H), 7.7 (s,1H), 7.4 (m, 2H), 2.4 (s, 6H) ppm.

Example P2 General Method for the Acylation of an Amino-Benzamide inParallel

Solution A was prepared by dissolving the amino-benzamide (0.65 mmol),3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Example I2) in the case of Compound No. A3 of Table A, in toluene (7.8ml). Solution B was prepared by dissolving the acid chloride (1.0 mol),2-fluoro-benzoyl chloride in the case of Compound No. A3 of Table A, intoluene (8 ml).

Solution A (0.3 ml, 25 μmol) was put in a well and solution B (0.4 ml,50 μmol) and diisopropylethylamine (Hunig's Base) (30 μl, 150 μmol) wereadded successively. The mixture was stirred at 55° C. for 16 hours. Themixture was diluted with a mixture of acetonitrile (0.6 ml) andN,N-dimethylacetamide (0.2 ml) and then purified by HPLC to give thedesired compound.

This general method was used to prepare a number of compounds (CompoundNo. A3 to A220 of Table A, Compound No. B2 to B15 of Table B, CompoundNo. D1 to D56 of Table D) in parallel.

Example P3 A Further General Method for the Acylation of anAmino-Benzamide in Parallel

Solution A was prepared by dissolving the amino-benzamide (0.65 mmol),3-amino-4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Example I16) in the case of Compound No. E43 of Table E, inN,N-dimethylacetamide (18.2 ml). Solution B was prepared by addingsodium hydride powder (9.6 mg, 0.4 mmol) in N,N-dimethylacetamide (2ml). Solution C was prepared by dissolving the acid chloride (0.025mol), 2-fluoro-benzoyl chloride in the case of Compound No. E43 of TableE, in N,N-dimethylacetamide (0.2 ml).

Solution A (0.7 ml, 25 μmol) was put in a well and Solution B (0.5 ml,100 mmol) was added. The mixture was stirred at ambient temperature for30 minutes. Then Solution C (0.2 ml, 25 μmol) was added and the mixturewas stirred at ambient temperature for 16 hours. The mixture was dilutedwith water and extracted three times with dichloromethane. The organicphases were combined, filtered and concentrated. The residue waspurified by HPLC to give the desired compound.

This general method was used to prepare a number of compounds (CompoundNo. E1 to E59 of Table E) in parallel.

Example P4 Preparation of3-cyano-5-(4′-cyano-benzoylamino)-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Compound No. B1 of Table B)

To a solution of5-amino-3-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(0.199 mg, 0.46 mmol) (Example I9) in tetrahydrofuran (3 ml) were addedsuccessively pyridine (0.117 ml, 1.45 mmol) and 4-cyano-benzoyl chloride(80 mg, 0.48 mmol). The reaction mixture was stirred for 2 hours atambient temperature. Aqueous sodium hydrogen carbonate (saturated) wasadded and the phases were separated. The aqueous phase was extractedtwice with ethyl acetate. The combined organic extracts were dried oversodium sulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: cyclohexane/ethyl acetate 2:1) togive Compound No. B1 of Table B (0.186 g, 71.9% yield). ¹H-NMR (400 MHz,CHCl₃): 8.45 (s, 1H), 8.36 (s, 1H), 8.27 (s, 1H), 8.00 (m, 3H), 7.84 (m,2H), 7.63 (s, 1H), 7.37 (s, 2H), 2.34 (s, 6H) ppm.

Analogous precedures were used to prepare the following compounds:Compound No. F1 and F2 of Table F and Compound No. G1 to G3 of Table G.

Example P5 Preparation of4-cyano-3-[(4′-cyano-benzoyl)-ethyl-amino]-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Compound No. C43 of Table C)

To a solution of4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-ethylamino-benzamide(198 mg, 0.43 mmol) (Example I4) in tetrahydrofuran (5 ml) were addedsuccessively pyridine (0.138 ml, 1.72 mmol) and 4-cyano-benzoyl chloride(0.214 mg, 1.29 mmol). The reaction mixture was heated to 50° C. for 16hours. The reaction mixture was allowed to cool to ambient temperature.A second portion of 4-cyano-benzoyl chloride (0.107 mg, 0.645 mmol),pyridine (0.138 ml, 1.72 mmol) were added and heating repeated at 90° C.for 2 hours. The reaction mixture was allowed to cool to ambienttemperature and then partitioned between aqueous sodium hydrogencarbonate (1M) and ethyl acetate. The aqueous phase was extracted twicewith ethyl acetate. The combine organic phases were dried over sodiumsulfate and concentrated. The residue was purified by columnchromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:4) togive Compound No. C43 of Table C (0.24 g, 94% yield).

Analogous precedures were used to prepare the following compounds:Compound No. C41 and C42 of Table C.

Example P6 Alternative preparation of3-benzoylamino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide(Compound No. D15 of Table D)

To a solution of3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide(68 mg, 0.15 mmol) (Example I12) in tetrahydrofuran (2 ml) were addedpyridine (36 μl, 0.45 mmol) and benzoyl chloride (21 μl, 0.18 mmol). Thereaction mixture was heated in a microwave at 140° C. for 30 minutes.The reaction mixture was allowed to cool to ambient temperature. Asecond portion of benzoyl chloride (21 μl, 0.18 mmol) was added andheating repeated at 140° C. for 30 minutes. The reaction mixture wasallowed to cool to ambient temperature and then partitioned betweensodium hydrogen carbonate (1M) and ethyl acetate. The aqueous phase wasextracted twice with ethyl acetate. The combined organic phases weredried over sodium sulfate and concentrated. The residue was purified byreverse-phase chromatography (eluent: trifluoroaceticacid/water/acetonitrile 1:4:5 to 1:1:8) to give Compound No. D15 ofTable D (0.024 g, 28% yield). ¹H-NMR (400 MHz, CDCl₃): 2.28 (6H, s),7.33 (2H, s), 7.45-7.96 (9H, m) ppm.

Example P7 Alternative preparation of3-benzamido-4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(Compound No. E36 of Table E)

To a solution of3-amino-4-cyano-2,5-difluoro-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide(70 mg, 0.15 mmol) (Example I16) in chloroform (0.75 ml) were added1,8-diazabicycloundec-7-ene (“DBU”) (49 μl, 0.33 mmol) and benzoylchloride (17 μl, 0.15 mmol). The reaction mixture was heated in amicrowave to 140° C. for 30 minutes. Two further portions of benzoylchloride (17 μl, 0.15 mmol) were added and heating continued at 140° C.for 30 minutes each time. The reaction mixture was partitioned betweenwater and chloroform. The aqueous phase was extracted twice withchloroform. The combined organic phases were dried over sodium sulfateand concentrated. The residue was purified by reverse-phasechromatography (eluent:trifluoroacetic acid/water/acetonitrile 1:4:5 to1:1:8) to give Compound No. E36 of Table E (0.013 g, 15% yield) as anoff-white solid. M.p. 245-248° C. ¹H-NMR (400 MHz, CDCl₃): 2.28 (6H, s),7.38 (2H, s), 7.15-8.1 (8H, m) ppm.

The following methods were used for HPLC-MS analysis:Method A: Method (Water Alliance 2795 LC) with the following HPLCgradient conditions(Solvent A: 0.1% of formic acid in water/acetonitrile (9:1) and SolventB: 0.1% of formic acid in acetonitrile)

Time (minutes) A (%) B (%) Flow rate (ml/min) 0 90 10 1.7 2.5 0 100 1.72.8 0 100 1.7 2.9 90 10 1.7Type of column: Water atlantis dc18; Column length: 20 mm; Internaldiameter of column: 3 mm; Particle Size: 3 micron; Temperature: 40° C.Method B: Method (Agilent 1100er Series) with the following HPLCgradient conditions(Solvent A: 0.1% of formic acid in water/acetonitrile (9:1); Solvent B:0.1% of formic acid in acetonitrile; Solvent C, 0.1% formic acid inwater; Solvent D: 0.1% formic acid in water)

Time (minutes) A (%) B (%) C (%) D (%) Flow rate (ml/min) 0 90 10 0 01.7 2.5 0 100 0 0 1.7 2.8 0 100 0 0 1.7 2.9 90 10 0 0 1.7Type of column: Water atlantis dc 18; Column length: 20 mm; Internaldiameter of column: 3 mm; Particle Size: 3 micron; Temperature: 40° C.

The characteristic values obtained for each compound were the retentiontime (“RT”, recorded in minutes) and the molecular ion, typically thecation MH⁺, as listed in Tables A and B.

TABLE A Compounds of formula (Ia): (Ia)

Comp RT min M.p. No. Q¹ Q² (method) MH+ (° C.) A1 4-cyano-2,6-dimethyl-4- — — — phenyl- (heptafluoroprop- 2-yl)-phenyl- A32-fluoro- 2,6-dimethyl-4- 2.07 (B) 556.1 — phenyl- (heptafluoroprop-2-yl)-phenyl- A4 2-methyl- 2,6-dimethyl-4- 2.0 (B) 552.1 — phenyl-(heptafluoroprop- 2-yl)-phenyl- A5 2-chloro- 2,6-dimethyl-4- 2.0 (B)572.1 — phenyl- (heptafluoroprop- 2-yl)-phenyl- A6 4-nitro-phenyl-2,6-dimethyl-4- 2.01 (B) 583.1 — (heptafluoroprop- 2-yl)-phenyl- A72-methylthio- 2,6-dimethyl-4- 2.2 (B) 652.1 — 4- (heptafluoroprop-trifluoromethyl- 2-yl)-phenyl- phenyl- A8 4-N,N- 2,6-dimethyl-4- 2.1 (B)581.2 — dimethyl- (heptafluoroprop- amino-phenyl- 2-yl)-phenyl- A95-chloro-2- 2,6-dimethyl-4- 2.17 (B) 590.1 — fluoro-phenyl-(heptafluoroprop- 2-yl)-phenyl- A10 furan-2-yl- 2,6-dimethyl-4- 1.9 (B)528.1 — (heptafluoroprop- 2-yl)-phenyl- A11 4- 2,6-dimethyl-4- 2.18 (B)622.1 — trifluoromethoxy- (heptafluoroprop- phenyl- 2-yl)-phenyl- A124-fluoro-3- 2,6-dimethyl-4- 2.17 (B) 624.1 — trifluoromethyl-(heptafluoroprop- phenyl- 2-yl)-phenyl- A13 4-trifluoro- 2,6-dimethyl-4-2.15 (B) 606.1 — methyl-phenyl- (heptafluoroprop- 2-yl)-phenyl- A142-methoxy- 2,6-dimethyl-4- 2.4 (B) 568.1 — phenyl- (heptafluoroprop-2-yl)-phenyl- A15 phenyl- 2,6-dimethyl-4- 2.0 (B) 538.1 —(heptafluoroprop- 2-yl)-phenyl- A16 4-fluoro- 2,6-dimethyl-4- 2.02 (B)556.1 — phenyl- (heptafluoroprop- 2-yl)-phenyl- A17 2-trifluoro-2,6-dimethyl-4- 2.02 (B) 606.1 — methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- A18 2,3-difluoro- 2,6-dimethyl-4- 2.07 (B) 574.1 — phenyl-(heptafluoroprop- 2-yl)-phenyl- A19 4-methoxy- 2,6-dimethyl-4- 2.0 (B)596.1 — carbonyl- (heptafluoroprop- phenyl- 2-yl)-phenyl- A202-fluoro-5- 2,6-dimethyl-4- 2.19 (B) 624.1 — trifluoromethyl-(heptafluoroprop- phenyl- 2-yl)-phenyl- A23 2-fluoro- 2,6-diethyl-4-2.19 (B) 584.2 — phenyl- (heptafluoroprop- 2-yl)-phenyl- A24 2-methyl-2,6-diethyl-4- 2.2 (B) 580.2 — phenyl- (heptafluoroprop- 2-yl-phenyl A252-chloro- 2,6-diethyl-4- 2.2 (B) 600.1 — phenyl- (heptafluoroprop-2-yl)-phenyl- A26 4-nitro-phenyl- 2,6-diethyl-4- 2.1 (B) 611.1 —(heptafluoroprop- 2-yl)-phenyl- A27 2-methylthio- 2,6-diethyl-4- 2.3 (B)680.1 — 4- (heptafluoroprop- trifluoromethyl- 2-yl)-phenyl- phenyl- A285-chloro-2- 2,6-diethyl-4- 2.3 (B) 618.1 — fluoro-phenyl-(heptafluoroprop- 2-yl)-phenyl- A29 furan-2-yl- 2,6-diethyl-4- 2.0 (B)556.1 — (heptafluoroprop- 2-yl)-phenyl- A30 4-trifluoro- 2,6-diethyl-4-2.3 (B) 650.1 — methoxy- (heptafluoroprop- phenyl- 2-yl)-phenyl- A314-fluoro-3- 2,6-diethyl-4- 2.3 (B) 652.1 — trifluoromethyl-(heptafluoroprop- phenyl- 2-yl)-phenyl- A32 4- 2,6-diethyl-4- 2.3 (B)634.1 — trifluoromethyl- (heptafluoroprop- phenyl- 2-yl)-phenyl- A33phenyl- 2,6-diethyl-4- 2.1 (B) 566.2 — (heptafluoroprop- 2-yl)-phenyl-A34 4-fluoro- 2,6-diethyl-4- 2.1 (B) 584.2 — phenyl- (heptafluoroprop-2-yl)-phenyl- A35 2- 2,6-diethyl-4- 2.1 (B) 634.1 — trifluoromethyl-(heptafluoroprop- phenyl- 2-yl)-phenyl- A36 4-methyl- 2,6-diethyl-4- 2.0(B) 588.1 — 1,2,3- (heptafluoroprop- thiadiazol-5-yl- 2-yl)-phenyl- A372,3-difluoro- 2,6-diethyl-4- 2.2 (B) 602.1 — phenyl- (heptafluoroprop-2-yl)-phenyl- A38 4-methoxy- 2,6-diethyl-4- 2.1 (B) 624.2 — carbonyl-(heptafluoroprop- phenyl- 2-yl)-phenyl- A39 2-fluoro-5- 2,6-diethyl-4-2.3 (B) 652.1 — trifluoromethyl- (heptafluoroprop- phenyl- 2-yl)-phenyl-A41 2-fluoro- 2,6-diethyl-4- 2.3 (A) 634.1 — phenyl- (nonafluorobut-2-yl)-phenyl- A42 2-methyl 2,6-diethyl-4- 2.2 (A) 630.2 — phenyl-(nonafluorobut- 2-yl)-phenyl- A43 2-chloro- 2,6-diethyl-4- 2.2 (A) 650.1— phenyl- (nonafluorobut- 2-yl)-phenyl- A44 4-cyano- 2,6-diethyl-4- 2.1(A) 641.2 — phenyl- (nonafluorobut- 2-yl)-phenyl- A45 furan-2-yl-2,6-diethyl-4- 2.1 (A) 606.1 — (nonafluorobut- 2-yl)-phenyl- A464-trifluoro- 2,6-diethyl-4- 2.3 (A) 700.1 — methoxy- (nonafluorobut-phenyl- 2-yl)-phenyl- A47 4-fluoro-3- 2,6-diethyl-4- 2.3 (A) 702.1 —trifluoromethyl- (nonafluorobut- phenyl- 2-yl)-phenyl- A48 4-2,6-diethyl-4- 2.3 (A) 684.1 — trifluoromethyl- (nonafluorobut- phenyl-2-yl)-phenyl- A49 2-trifluoro- 2,6-diethyl-4- 2.3 (A) 700.1 — methoxy-(nonafluorobut- phenyl- 2-yl)-phenyl- A50 2-methoxy- 2,6-diethyl-4- 2.4(A) 646.2 — phenyl- (nonafluorobut- 2-yl)-phenyl- A51 phenyl-2,6-diethyl-4- 2.2 (A) 616.2 — (nonafluorobut- 2-yl)-phenyl- A524-fluoro- 2,6-diethyl-4- 2.2 (A) 634.1 — phenyl- (nonafluorobut-2-yl)-phenyl- A53 2- 2,6-diethyl-4- 2.2 (A) 684.1 — trifluoromethyl-(nonafluorobut- phenyl- 2-yl)-phenyl- A54 2-chloro-4- 2,6-diethyl-4- 2.2(A) 668.1 — fluoro-phenyl- (nonafluorobut- 2-yl)-phenyl- A55 4-methyl-2,6-diethyl-4- 2.1 (A) 638.1 — 1,2,3- (nonafluorobut- thiadiazol-5-yl-2-yl)-phenyl- A56 2,3-difluoro- 2,6-diethyl-4- 2.3 (A) 652.1 — phenyl-(nonafluorobut- 2-yl)-phenyl- A57 4-methoxy- 2,6-diethyl-4- 2.2 (A)674.2 — carbonyl- (nonafluorobut- phenyl- 2-yl)-phenyl- A58 2-fluoro-5-2,6-diethyl-4- 2.4 (A) 702.1 — trifluoromethyl- (nonafluorobut- phenyl-2-yl)-phenyl- A61 2-fluoro- 2-ethyl-6-methyl- 2.2 (A) 620.1 — phenyl-4-(nonafluorobut- 2-yl)-phenyl- A62 2-chloro- 2-ethyl-6-methyl- 2.2 (A)636.1 — phenyl- 4-(nonafluorobut- 2-yl)-phenyl- A63 4-cyano-2-ethyl-6-methyl- 2.1 (A) 627.1 — phenyl- 4-(nonafluorobut-2-yl)-phenyl- A64 2-chloro-4- 2-ethyl-6-methyl- 2.3 (A) 654.1 —nitro-phenyl- (nonafluorobut- 2-yl)-phenyl- A65 furan-2-yl-2-ethyl-6-methyl- 2.0 (A) 592.1 — 4-(nonafluorobut- 2-yl)-phenyl- A664-trifluoro- 2-ethyl-6-methyl- 2.3 (A) 686.1 — methoxy- (nonafluorobut-phenyl- 2-yl)-phenyl- A67 4-fluoro-3- 2-ethyl-6-methyl- 2.3 (A) 688.1 —trifluoro- 4-(nonafluorobut- methyl-phenyl- 2-yl)-phenyl- A68 4-2-ethyl-6-methyl- 2.3 (A) 670.1 — trifluoromethyl- 4-(nonafluorobut-phenyl- 2-yl)-phenyl- A69 2-trifluoro- 2-ethyl-6-methyl- 2.2 (A) 686.1 —methoxy- 4-(nonafluorobut- phenyl- 2-yl)-phenyl- A70 2-methoxy-2-ethyl-6-methyl- 2.4 (A) 632.2 — phenyl- 4-(nonafluorobut-2-yl)-phenyl- A71 phenyl- 2-ethyl-6-methyl- 2.1 (A) 602.1 —4-(nonafluorobut- 2-yl)-phenyl- A72 4-fluoro- 2-ethyl-6-methyl- 2.1 (A)620.1 — phenyl- 4-(nonafluorobut- 2-yl)-phenyl- A73 2- 2-ethyl-6-methyl-2.2 (A) 670.1 — trifluoromethyl- 4-(nonafluorobut- phenyl- 2-yl)-phenyl-A74 2-chloro-4- 2-ethyl-6-methyl- 2.2 (A) 654.1 — fluoro-phenyl-4-(nonafluorobut- 2-yl)-phenyl- A75 4-methyl- 2-ethyl-6-methyl- 2.0 (A)624.1 — 1,2,3- 4-(nonafluorobut- thiadiazol-5-yl- 2-yl)-phenyl- A762,3-difluoro- 2-ethyl-6-methyl- 2.2 (A) 638.1 — phenyl-4-(nonafluorobut- 2-yl)-phenyl- A77 4-methoxy- 2-ethyl-6-methyl- 2.1 (A)660.1 — carbonyl- 4-(nonafluorobut- phenyl- 2-yl)-phenyl- A782-fluoro-5- 2-ethyl-6-methyl- 2.3 (A) 688.1 — trifluoromethyl-4-(nonafluorobut- phenyl- 2-yl)-phenyl- A80 2-fluoro-5- 2-bromo-6- 2.2(B) 688 — trifluoro- methyl-4- methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- A81 2-fluoro- 2-bromo-6- 2.1 (B) 620 — phenyl- methyl-4-(heptafluoroprop- 2-yl)-phenyl- A82 2-methyl- 2-bromo-6- 2.1 (B) 616 —phenyl- methyl-4- (heptafluoroprop- 2-yl)-phenyl- A83 2-chloro-2-bromo-6- 2.1 (B) 636 — phenyl- methyl-4- (heptafluoroprop-2-yl)-phenyl- A84 4-cyano- 2-bromo-6- 2.0 (B) 627 — phenyl- methyl-4-(heptafluoroprop- 2-yl)-phenyl- A85 4-nitro-phenyl- 2-bromo-6- 2.0 (B)647 — methyl-4- (heptafluoroprop- 2-yl)-phenyl- A86 5-chloro-2-2-bromo-6- 2.2 (B) 654 — fluoro-phenyl- methyl-4- (heptafluoroprop-2-yl)-phenyl- A87 2-chloro-4- 2-bromo-6- 2.1 (B) 681 — nitro-phenyl-methyl-4- (heptafluoroprop- 2-yl)-phenyl- A88 furan-2-yl- 2-bromo-6- 1.9(B) 592 — methyl-4- (heptafluoroprop- 2-yl)-phenyl- A89 4-trifluoro-2-bromo-6- 2.2 (B) 686 — methoxy- methyl-4- phenyl- (heptafluoroprop-2-yl)-phenyl- A90 4-fluoro-3- 2-bromo-6- 2.2 (B) 688 — trifluoro-methyl-4- methyl-phenyl- (heptafluoroprop- 2-yl)-phenyl- A914-trifluoro- 2-bromo-6- 2.2 (B) 670 — methyl-phenyl- methyl-4-(heptafluoroprop- 2-yl)-phenyl- A92 2-trifluoro- 2-bromo-6- 2.1 (B) 686— methoxy- methyl-4- phenyl- (heptafluoroprop- 2-yl)-phenyl- A932-methoxy- 2-bromo-6- 2.27 (B) 632 — phenyl- methyl-4- (heptafluoroprop-2-yl)-phenyl- A94 phenyl- 2-bromo-6- 2.02 (B) 602 — methyl-4-(heptafluoroprop- 2-yl)-phenyl- A95 4-fluoro- 2-bromo-6- 2.0 (B) 620 —phenyl- methyl-4- (heptafluoroprop- 2-yl)-phenyl- A96 2-trifluoro-2-bromo-6- 2.1 (B) 670 — methyl-phenyl- methyl-4- (heptafluoroprop-2-yl)-phenyl- A97 2-chloro-4- 2-bromo-6- 2.1 (B) 654 — fluoro-phenyl-methyl-4- (heptafluoroprop- 2-yl)-phenyl- A98 4-methyl- 2-bromo-6- 1.9(B) 624 — 1,2,3- methyl-4- thiadiazol-5-yl- (heptafluoroprop-2-yl)-phenyl- A99 2,3-difluoro- 2-bromo-6- 2.1 (B) 638 — phenyl-methyl-4- (heptafluoroprop- 2-yl)-phenyl- A100 4-methoxy- 2-bromo-6- 2.0(B) 660 — carbonyl- methyl-4- phenyl- (heptafluoroprop- 2-yl)-phenyl-A101 2-fluoro- 2-bromo-6- 2.2 (B) 670 — phenyl- methyl-4-(nonafluorobut- 2-yl)-phenyl- A102 2-methyl- 2-bromo-6- 2.2 (B) 666 —phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl- A103 2-chloro-2-bromo-6- 2.2 (B) 686 — phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl-A104 4-cyano- 2-bromo-6- 2.1 (B) 677 — phenyl- methyl-4- (nonafluorobut-2-yl)-phenyl- A105 4-nitro-phenyl- 2-bromo-6- 2.1 (B) 697 — methyl-4-(nonafluorobut- 2-yl)-phenyl- A106 5-chloro-2- 2-bromo-6- 2.3 (B) 704 —fluoro-phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl- A107 2-chloro-4-2-bromo-6- 2.3 (B) 731 — ro-phenyl- methyl-4- (nonafluorobut-2-yl)-phenyl- A108 furan-2-yl- 2-bromo-6- 2.0 (B) 642 — methyl-4-(nonafluorobut- 2-yl)-phenyl- A109 4-trifluoro- 2-bromo-6- 2.3 (B) 736 —methoxy- methyl-4- phenyl- (nonafluorobut- 2-yl)-phenyl- A1104-fluoro-3- 2-bromo-6- 2.3 (B) 738 — trifluoro- methyl-4- methyl-phenyl-(nonafluorobut- 2-yl)-phenyl- A111 4-trifluoro- 2-bromo-6- 2.3 (B) 720 —methyl-phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl- A112 2-trifluoro-2-bromo-6- 2.2 (B) 736 — methoxy- methyl-4- phenyl- (nonafluorobut-2-yl)-phenyl- A113 2-methoxy- 2-bromo-6- 2.35 (B) 682 — phenyl-methyl-4- (nonafluorobut- 2-yl)-phenyl- A114 phenyl- 2-bromo-6- 2.1 (B)652 — methyl-4- (nonafluorobut- 2-yl)-phenyl- A115 4-fluoro- 2-bromo-6-2.1 (B) 670 — phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl- A1162-chloro-4- 2-bromo-6- 2.2 (B) 704 — fluoro-phenyl- methyl-4-(nonafluorobut- 2-yl)-phenyl- A117 4-methyl- 2-bromo-6- 2.0 (B) 674 —1,2,3- methyl-4- thiadiazol-5-yl (nonafluorobut- 2-yl)-phenyl- A1182,3-difluoro- 2-bromo-6- 2.2 (B) 688 — phenyl- methyl-4- (nonafluorobut-2-yl)-phenyl- A119 4-methoxy- 2-bromo-6- 2.13 (B) 710 — carbonyl-methyl-4- phenyl- (nonafluorobut- 2-yl)-phenyl- A120 2-fluoro-5-2-bromo-6- 2.3 (B) 738 — trifluoro- methyl-4- methyl-phenyl-(nonafluorobut- 2-yl)-phenyl- A121 2-fluoro- 2-bromo-6- 2.2 (B) 634 —phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A122 2-methyl-2-bromo-6- 2.1 (B) 630.1 — phenyl- ethyl-4- (heptafluoroprop-2-yl)-phenyl- A123 2-chloro- 2-bromo-6- 2.1 (B) 650 — phenyl- ethyl-4-(heptafluoroprop- 2-yl)-phenyl- A124 4-cyano- 2-bromo-6- 2.1 (B) 641 —phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A125 4-nitro-phenyl-2-bromo-6- 2.1 (B) 661 — ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A1265-chloro-2- 2-bromo-6- 2.3 (B) 668 — fluoro-phenyl- ethyl-4-(heptafluoroprop- 2-yl)-phenyl- A127 2-chloro-4- 2-bromo-6- 2.1 (B) 695— nitro-phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A128furan-2-yl- 2-bromo-6- 2.0 (B) 606 — ethyl-4- (heptafluoroprop-2-yl)-phenyl- A129 4-trifluoro- 2-bromo-6- 2.3 (B) 700 — methoxy-ethyl-4- phenyl- (heptafluoroprop- 2-yl)-phenyl- A130 4-fluoro-3-2-bromo-6- 2.25 (B) 702 — trifluoro- ethyl-4- methyl-phenyl-(heptafluoroprop- 2-yl)-phenyl- A131 4-trifluoro- 2-bromo-6- 2.23 (B)684 — methyl-phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A1322-trifluoro- 2-bromo-6- 2.2 (B) 700 — methoxy- ethyl-4- phenyl-(heptafluoroprop- 2-yl)-phenyl- A133 2-methoxy- 2-bromo-6- 2.33 (B) 646— phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A134 phenyl-2-bromo-6- 2.1 (B) 616 — ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A1354-fluoro- 2-bromo-6- 2.1 (B) 634 — phenyl- ethyl-4- (heptafluoroprop-2-yl)-phenyl- A136 2-trifluoro- 2-bromo-6- 2.1 (B) 684 — methyl-phenyl-ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A137 2-chloro-4- 2-bromo-6- 2.2(B) 668 — fluoro-phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A1384-methyl- 2-bromo-6- 2.0 (B) 638 — 1,2,3- ethyl-4- thiadiazol-5-yl-(heptafluoroprop- 2-yl)-phenyl- A139 2,3-difluoro- 2-bromo-6- 2.16 (B)652 — phenyl- ethyl-4- (heptafluoroprop- 2-yl)-phenyl- A140 4-methoxy-2-bromo-6- 2.1 (B) 674 — carbonyl- ethyl-4- phenyl- (heptafluoroprop-2-yl)-phenyl- A141 2-fluoro-5- 2-bromo-6- 2.28 (B) 702 — trifluoro-ethyl-4- methyl-phenyl- (heptafluoroprop- 2-yl)-phenyl- A142 2-methyl-2-bromo-6- 2.2 (B) 680.1 — phenyl- ethyl-4- (nonafluorobut-2-yl)-phenyl- A143 2-chloro- 2-bromo-6- 2.2 (B) 700 — phenyl- ethyl-4-(nonafluorobut- 2-yl)-phenyl- A144 4-cyano- 2-bromo-6- 2.1 (B) 691 —phenyl- ethyl-4- (nonafluorobut- 2-yl)-phenyl- A145 4-nitro-phenyl-2-bromo-6- 2.19 (B) 711 — ethyl-4- (nonafluorobut- 2-yl)-phenyl- A1465-chloro-2- 2-bromo-6- 2.3 (B) 718 — fluoro-phenyl- ethyl-4-(nonafluorobut- 2-yl)-phenyl- A147 2-chloro-4- 2-bromo-6- 2.2 (B) 745 —nitro-phenyl- ethyl-4- (nonafluorobut- 2-yl)-phenyl- A148 furan-2-yl-2-bromo-6- 2.1 (B) 656 — ethyl-4- (nonafluorobut- 2-yl)-phenyl- A1494-trifluoro- 2-bromo-6- 2.3 (B) 750 — methoxy- ethyl-4- phenyl-(nonafluorobut- 2-yl)-phenyl- A150 4-fluoro-3- 2-bromo-6- 2.3 (B) 752 —trifluoro- ethyl-4- methyl-phenyl- (nonafluorobut- 2-yl)-phenyl- A1514-trifluoro- 2-bromo-6- 2.3 (B) 734 — methyl-phenyl- ethyl-4-(nonafluorobut- 2-yl)-phenyl- A152 2-trifluoro- 2-bromo-6- 2.29 (B) 750— methoxy- ethyl-4- phenyl- (nonafluorobut- 2-yl)-phenyl- A1532-methoxy- 2-bromo-6- 2.4 (B) 696 — phenyl- ethyl-4- (nonafluorobut-2-yl)-phenyl- A154 phenyl- 2-bromo-6- 2.18 (B) 666 — ethyl-4-(nonafluorobut- 2-yl)-phenyl- A155 4-fluoro- 2-bromo-6- 2.2 (B) 684 —phenyl- ethyl-4- (nonafluorobut- 2-yl)-phenyl- A156 2-trifluoro-2-bromo-6- 2.2 (B) 734 — methyl-phenyl- ethyl-4- (nonafluorobut-2-yl)-phenyl- A157 2-chloro-4- 2-bromo-6- 2.2 (B) 718 — fluoro-phenyl-ethyl-4- (nonafluorobut- 2-yl)-phenyl- A158 4-methyl- 2-bromo-6- 2.1 (B)688 — 1,2,3- ethyl-4- thiadiazol-5-yl- (nonafluorobut- 2-yl)-phenyl-A159 2,3-difluoro- 2-bromo-6- 2.2 (B) 702 — phenyl- ethyl-4-(nonafluorobut- 2-yl)-phenyl- A160 4-methoxy- 2-bromo-6- 2.2 (B) 724 —carbonyl- ethyl-4- phenyl- (nonafluorobut- 2-yl)-phenyl- A1612-fluoro-5- 2-bromo-6- 2.4 (B) 752 — trifluoro- ethyl-4- phenyl-(nonafluorobut- 2-yl)-phenyl- A162 2-fluoro- 2-bromo-6- 2.3 (B) 684 —phenyl- ethyl-4- (nonafluorobut- 2-yl)-phenyl- A163 2-fluoro- 2-methoxy-1.9 (A) 586.1 — phenyl- methyl-6- methyl-4- (heptafluoro- prop-2-yl)-phenyl- A164 2-methyl- 2-methoxy- 1.8 (A) 582.2 — phenyl- methyl-6-methyl-4- (heptafluoro- prop-2-yl)- phenyl- A165 2-chloro- 2-methoxy-1.8 (A) 602.1 — phenyl- methyl-6- methyl-4- (heptafluoro- prop-2-yl)-phenyl- A166 4-cyano- 2-methoxy- 1.8 (A) 613.1 — phenyl- methyl-6-methyl-4- (heptafluoro- prop-2-yl)- phenyl- A167 4-nitro-phenyl-2-methoxy- 1.9 (A) 582.2 — methyl-6- methyl-4- (heptafluoro- prop-2-yl)-phenyl- A168 2-methyl-4- 2-methoxy- 1.9 (A) 600.1 — fluoro-phenyl-methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl- A169 5-chloro-2-2-methoxy- 2.0 (A) 620.1 — fluoro-phenyl- methyl-6- methyl-4-(heptafluoro- prop-2-yl)- phenyl- A170 furan-2-yl- 2-methoxy- 1.7 (A)558.1 — methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl- A1714-trifluoro- 2-methoxy- 2.0 (A) 652.1 — methoxy- methyl-6- phenyl-methyl-4- (heptafluoro- prop-2-yl)- phenyl- A172 4-trifluoro- 2-methoxy-2.0 (A) 636.1 — methyl-phenyl- methyl-6- methyl-4- (heptafluoro-prop-2-yl)- phenyl- A173 2-trifluoro- 2-methoxy- 1.9 (A) 652.1 —methoxy- methyl-6- phenyl- methyl-4- (heptafluoro- prop-2-yl)- phenyl-A174 2-methoxy- 2-methoxy- 2.1 (A) 598.1 — phenyl- methyl-6- methyl-4-(heptafluoro- prop-2-yl)- phenyl- A175 2-trifluoro- 2-methoxy- 1.9 (A)636.1 — methyl-phenyl- methyl-6- methyl-4- (heptafluoro- prop-2-yl)-phenyl- A176 2-chloro-4- 2-methoxy- 1.9 (A) 620.1 — fluoro-phenyl-methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl- A177 4-methyl-2-methoxy- 1.7 (A) 590.1 — 1,2,3- methyl-6- thiadiazol-5-yl- methyl-4-(heptafluoro- prop-2-yl)- phenyl- A178 2,3-difluoro- 2-methoxy- 1.9 (A)604.1 — phenyl- methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl-A179 2,4-difluoro- 2-methoxy- 1.9 (A) 604.1 — phenyl- methyl-6-methyl-4- (heptafluoro- prop-2-yl)- phenyl- A180 2-fluoro-5- 2-methoxy-2.0 (A) 654.1 — trifluoro- methyl-6- methyl-phenyl- methyl-4-(heptafluoro- prop-2-yl)- phenyl- A181 2,6-dichloro-5- 2,6-dimethyl-4- —— 126 fluoro-pyrid-3- (heptafluoroprop- yl- 2-yl)-phenyl- A1822-fluoro-4- 2,6-dimethyl-4- — — 197 cyano-phenyl- (heptafluoroprop-2-yl)-phenyl- A183 2,3-dichloro- 2,6-dimethyl-4- — — 110 phenyl-(heptafluoroprop- 2-yl)-phenyl- A184 2-fluoro-pyrid- 2,6-dimethyl-4- — —189 3-yl- (heptafluoroprop- 2-yl)-phenyl- A185 2,3,4,5,6-2,6-dimethyl-4- — — 261 pentafluoro- (heptafluoroprop- phenyl-2-yl)-phenyl- A186 2,3,5,6- 2,6-dimethyl-4- — — 190 tetrafluoro-(heptafluoroprop- phenyl- 2-yl)-phenyl- A187 2-fluoro-4-2-ethyl-6-methyl- — — 198 cyano-phenyl- 4-(nonafluorobut- 2-yl)-phenyl-A188 2-methyl-3- 2-ethyl-6-methyl- — — 135 chloro-phenyl-4-(nonafluorobut- 2-yl)-phenyl- A189 4-cyano- 2-methoxy- — — 192 phenyl-methyl- 6-methyl-4- (nonafluorobut- 2-yl)-phenyl- A190 2-chloro-pyrid-2-ethyl-6-methyl- — — 119 3-yl- 4-(nonafluorobut- 2-yl)-phenyl- A1913-chloro- 2-ethyl-6-methyl- — — 206 phenyl- 4-(nonafluorobut-2-yl)-phenyl- A192 pyrid-3-yl- 2-ethyl-6-methyl- — — 1224-(nonafluorobut- 2-yl)-phenyl- A193 3,5-dichloro- 2-ethyl-6-methyl- — —164 phenyl- 4-(nonafluorobut- 2-yl)-phenyl- A194 2-fluoro-pyrid-2-ethyl-6-methyl- — — 192 3-yl- 4-(nonafluorobut- 2-yl)-phenyl- A1952-methyl- 2-ethyl-6-methyl- — — 120 pyrid-3-yl- 4-(nonafluorobut-2-yl)-phenyl- A196 3,5-difluoro- 2-ethyl-6-methyl- — — 173 phenyl-4-(nonafluorobut- 2-yl)-phenyl- A197 3,5-dimethyl- 2-ethyl-6-methyl- — —138 phenyl- 4-(nonafluorobut- 2-yl)-phenyl- A198 6-cyano-pyrid-2-ethyl-6-methyl- — — 151 3-yl- 4-(nonafluorobut- 2-yl)-phenyl- A1994-cyano- 2,6-diethyl-4- — — 269 phenyl- (heptafluoroprop- 2-yl)-phenyl-A200 2-chloro-pyrid- 2,6-dimethyl-4- — — 195 3-yl- (heptafluoroprop-2-yl)-phenyl- A201 2-methoxy- 2,6-dimethyl-4- — — 238 pyrid-3-yl-(heptafluoroprop- 2-yl)-phenyl- A202 5-bromo-pyrid- 2,6-dimethyl-4- — —235 3-yl- (heptafluoroprop- 2-yl)-phenyl- A203 5,6-dichloro-2,6-dimethyl-4- — — 253 pyrid-3-yl- (heptafluoroprop- 2-yl)-phenyl- A2042,3,5-triiodo- 2,6-dimethyl-4- — — 182.0 phenyl- (heptafluoroprop-2-yl)-phenyl- A205 2,3-dimethyl- 2,6-dimethyl-4- — — 209.0 phenyl-(heptafluoroprop- 2-yl)-phenyl- A206 2-methyl-3- 2,6-dimethyl-4- — —196.0 chloro-phenyl- (heptafluoroprop- 2-yl)-phenyl- A207 2,6-dichloro-2,6-dimethyl-4- — — 132.0 pyrid-3-yl- (heptafluoroprop- 2-yl)-phenyl-A208 2,3,4,5- 2,6-dimethyl-4- — — 164.0 tetrafluoro- (heptafluoroprop-phenyl- 2-yl)-phenyl- A209 2,3,4-trifluoro- 2,6-dimethyl-4- — — 233.0phenyl- (heptafluoroprop- 2-yl)-phenyl- A210 2-chloro-4- 2,6-dibromo-4-— — 212.0 fluoro-phenyl- (heptafluoroprop- 2-yl)-phenyl- A211 4-fluoro-2,6-dibromo-4- — — 249.0 phenyl- (heptafluoroprop- 2-yl)-phenyl- A2124-cyano- 2,6-dibromo-4- — — 226 phenyl- (heptafluoroprop- 2-yl)-phenyl-A213 2-chloro-4- 2-methoxy- — — 95 cyano-phenyl- methyl- 6-methyl-4-(nonafluoro- but-2-yl)-phenyl- A214 2,3,6-trifluoro- 2,6-dimethyl-4- — —126 phenyl- (heptafluoroprop- 2-yl)-phenyl- A215 4-nitro-phenyl-2,6-diethyl-4- 2.19 (A) 661 — (nonafluorobut- 2-yl)-phenyl- A2162-chloro-4- 2,6-diethyl-4- 2.23 (A) 695 — nitro-phenyl-4-(nonafluorobut- 2-yl)-phenyl- A217 5-chloro-2- 2-ethyl-6- 2.3 (A) 654— fluoro-phenyl- methyl-4- (nonafluorobut- 2-yl)-phenyl- A218 phenyl-2-methoxy- — — 78 methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl-A219 4-fluoro- 2-methoxy- — — 86 phenyl- methyl-6- methyl-4-(heptafluoro- prop-2-yl)- phenyl- A220 4-methyl- 2-methoxy- 1.9 (A)582.2 — phenyl- methyl-6- methyl-4- (heptafluoro- prop-2-yl)- phenyl-

TABLE B Compounds of formula (Ib): (Ib)

Comp RT min No. Q¹ Q² (method) MH+ B1 4-cyano- 2,6-dimethyl-4- — —phenyl- (heptafluoroprop-2-yl)- phenyl- B2 2-fluoro- 2,6-dimethyl-4-2.06 (B)  556.1 phenyl- (heptafluoroprop-2-yl)- phenyl- B3 2-methyl-2,6-dimethyl-4- 2.1 (B) 552.1 phenyl- (heptafluoroprop-2-yl)- phenyl- B42-chloro- 2,6-dimethyl-4- 2.1 (B) 572.1 phenyl- (heptafluoroprop-2-yl)-phenyl- B5 2-methylthio- 2,6-dimethyl-4- 2.2 (B) 652.1 4-tri-(heptafluoroprop-2-yl)- fluoromethyl- phenyl- phenyl- B6 5-chloro-2-2,6-dimethyl-4- 2.2 (B) 590.1 fluoro-phenyl- (heptafluoroprop-2-yl)-phenyl- B7 furan-2-yl- 2,6-dimethyl-4- 1.9 (B) 528.1(heptafluoroprop-2-yl)- phenyl- B8 4-trifluoro- 2,6-dimethyl-4- 2.2 (B)622.1 methoxy- (heptafluoroprop-2-yl)- phenyl- phenyl- B9 4-trifluoro-2,6-dimethyl-4- 2.2 (B) 606.1 methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- B10 2-trifluoro- 2,6-dimethyl-4- 2.1 (B) 622.1 methoxy-(heptafluoroprop-2-yl)- phenyl- phenyl- B11 phenyl- 2,6-dimethyl-4- 2.1(B) 538.1 (heptafluoroprop-2-yl)- phenyl- B12 4-fluoro- 2,6-dimethyl-4-2.1 (B) 556.1 phenyl- (heptafluoroprop-2-yl)- phenyl- B13 2-trifluoro-2,6-dimethyl-4- 2.1 (B) 606.1 methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- B14 4-methoxy- 2,6-dimethyl-4- 2.08 (B)  596.1 carbonyl-(heptafluoroprop-2-yl)- phenyl- phenyl- B15 2-fluoro-5- 2,6-dimethyl-4-2.2 (B) 624.1 trifluoro- (heptafluoroprop-2-yl)- methyl-phenyl- phenyl-

TABLE C Compounds of formula (Ia′): (Ia′)

Comp RT min No. R¹ Q¹ Q² (method) MH+ M.p. (° C.) C1 Me 2-fluoro-2,6-dimethyl-4- 1.77 (A) 570.1 phenyl- (heptafluoroprop-2- yl)-phenyl-C2 Me 2-methyl- 2,6-dimethyl-4- 1.9 (A) 566.2 phenyl-(heptafluoroprop-2- yl)-phenyl- C3 Me 2-chloro- 2,6-dimethyl-4- 1.86 (A)586.1 phenyl- (heptafluoroprop-2- yl)-phenyl- C4 Me 4-cyano-2,6-dimethyl-4- 1.8 (A) 577.1 phenyl- (heptafluoroprop-2- yl)-phenyl- C5Me 4-nitro-phenyl- 2,6-dimethyl-4- 1.8 (A) 597.1 (heptafluoroprop-2-yl)-phenyl- C6 Me 2-methylthio- 2,6-dimethyl-4- 2.0 (A) 666.14-trifluoro- (heptafluoroprop-2- methyl-phenyl- yl)-phenyl- C8 Me5-chloro-2- 2,6-dimethyl-4- 1.92 (A) 604.1 fluoro-phenyl-(heptafluoroprop-2- yl)-phenyl- C9 Me 2-chloro-4- 2,6-dimethyl-4- 1.91(A) 631.1 nitro-phenyl- (heptafluoroprop-2- yl)-phenyl- C10 Mefuran-2-yl- 2,6-dimethyl-4- 1.70 (A) 542.1 (heptafluoroprop-2-yl)-phenyl- C11 Me 4-trifluoro- 2,6-dimethyl-4- 1.98 (A) 636.1 methoxy-(heptafluoroprop-2- phenyl- yl)-phenyl- C12 Me 4-fluoro-3-2,6-dimethyl-4- 1.96 (A) 638.1 trifluoro- (heptafluoroprop-2- methylyl)-phenyl- phenyl- C13 Me 4-trifluoro- 2,6-dimethyl-4- 1.95 (A) 620.1methyl-phenyl- (heptafluoroprop-2- yl)-phenyl- C14 Me 2-trifluoro-2,6-dimethyl-4- 1.9 (A) 636.1 methoxy- (heptafluoroprop-2- phenyl-yl)-phenyl- C15 Me 2-methoxy- 2,6-dimethyl-4- 1.8 (A) 582.2 phenyl-(heptafluoroprop-2- yl)-phenyl- C16 Me phenyl- 2,6-dimethyl-4- 1.8 (A)552.1 (heptafluoroprop-2- yl)-phenyl- C17 Me 4-fluroo- 2,6-dimethyl-4-1.79 (A) 570.1 phenyl- (heptafluoroprop-2- yl)-phenyl- C18 Me2-trifluoro- 2,6-dimethyl-4- 1.92 (A) 620.1 methyl-phenyl-(heptafluoroprop-2- yl)-phenyl- C19 Me 2-chloro-4- 2,6-dimethyl-4- 1.9A) 604.1 fluoro-phenyl- (heptafluoroprop-2- yl)-phenyl- C20 Me 4-methyl-2,6-dimethyl-4- 1.8 (A) 574.1 1,2,3-thia- (heptafluoroprop-2-diazol-5-yl- yl)-phenyl- C21 Me 2,3-difluoro- 2,6-dimethyl-4- 1.9 (A)588.1 phenyl- (heptafluoroprop-2- yl)-phenyl- C23 Me 2-fluoro-5-2,6-dimethyl-4- 1.96 (A) 638.1 tri- (heptafluoroprop-2- fluoromethyl-yl)-phenyl- phenyl- C24 Me 2-fluoro- 2,6-diethyl-4- 1.9 (A) 598.2phenyl)- (heptafluoroprop-2- yl)-phenyl- C25 Me 2-methyl- 2,6-diethyl-4-2.0 (A) 594.2 phenyl- (heptafluoroprop-2- yl)-phenyl- C26 Me 2-chloro-2,6-diethyl-4- 2.0 (A) 614.1 phenyl- (heptafluoroprop-2- yl)-phenyl- C27Me 4-nitro-phenyl- 2,6-diethyl-4- 1.96 (A) 625.2 (heptafluoroprop-2-yl)-phenyl- C28 Me 4-N,N- 2,6-diethyl-4- 2.2 (A) 623.2 dimethyl-(heptafluoroprop-2- amino-phenyl- yl)-phenyl- C29 Me 5-chloro-2-2,6-diethyl-4- 2.0 (A) 632.1 fluoro-phenyl- (heptafluoroprop-2-yl)-phenyl- C30 Me 2-chloro-4- 2,6-diethyl-4- 2.0 (A) 659.1nitro-phenyl- (heptafluoroprop-2- yl)-phenyl- C31 Me 4-trifluoro-2,6-diethyl-4- 2.09 (A) 664.2 methoxy- (heptafluoroprop-2- phenyl-yl)-phenyl- C32 Me 4-trifluoro- 2,6-diethyl-4- 2.07 (A) 648.2methyl-phenyl- (heptafluoroprop-2- yl)-phenyl- C33 Me 2-trifluoro-2,6-diethyl-4- 2.0 (A) 664.2 methoxy- (heptafluoroprop-2- phenyl-yl)-phenyl- C34 Me 2-methoxy- 2,6-diethyl-4- 1.9 (A) 610.2 phenyl-(heptafluoroprop-2- yl)-phenyl- C35 Me phenyl- 2,6-diethyl-4- 1.92 (A)580.2 (heptafluoroprop-2- yl)-phenyl- C36 Me 4-fluoro- 2,6-diethyl-4-1.92 (A) 598.2 phenyl- (heptafluoroprop-2- yl)-phenyl- C37 Me2-trifluoro- 2,6-diethyl-4- 2.0 (A) 648.2 methyl-phenyl-(heptafluoroprop-2- yl)-phenyl- C38 Me 2-chloro-4- 2,6-diethyl-4- 2.04(A) 632.1 fluoro-phenyl- (heptafluoroprop-2- yl)-phenyl- C39 Me2,3-difluoro- 2,6-diethyl-4- 2.0 (A) 616.2 phenyl- (heptafluoroprop-2-yl)-phenyl- C40 Me 4-methoxy- 2,6-diethyl-4- 1.91 (A) 638.2 carbonyl-(heptafluoroprop-2- phenyl- yl)-phenyl- C41 Me 4-cyano- 2,6-diethyl-4- —— 187 phenyl- (heptafluoroprop-2- yl)-phenyl- C42 Et 4-fluoro-2,6-dimethyl-4- — — 93 phenyl- (heptafluoroprop-2- yl)-phenyl- C43 Et4-cyano- 2,6-dimethyl-4- — — 124 phenyl- (heptafluoroprop-2- yl)-phenyl-

TABLE D Compounds of formula (Ie): (Ie)

Comp RT min No. Q¹ Q² (method) MH+ D1 2-fluoro- 2,6-dimethyl-4- 1.81 (A)572.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D2 2-methyl-2,6-dimethyl-4- 1.8 (A) 568.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D32-chloro- 2,6-dimethyl-4- 1.8 (A) 588.1 phenyl- (heptafluoroprop-2-yl)-phenyl- D4 4-cyano- 2,6-dimethyl-4- 1.8 (A) 579.1 phenyl-(heptafluoroprop-2-yl)- phenyl- D5 4-nitro-phenyl- 2,6-dimethyl-4- 1.8(A) 599.1 (heptafluoroprop-2-yl)- phenyl- D6 2-methylthio-4-2,6-dimethyl-4- 2.01 (A) 668.1 trifluoromethyl- (heptafluoroprop-2-yl)-phenyl- phenyl- D7 4-N,N- 2,6-dimethyl-4- 1.9 (A) 597.2 dimethylamino-(heptafluoroprop-2-yl)- phenyl- phenyl- D8 5-chloro-2- 2,6-dimethyl-4-1.9 (A) 606.1 lfuoro-phenyl- (heptafluoroprop-2-yl)- phenyl- D92-chloro-4- 2,6-dimethyl-4- 1.9 (A) 633.1 nitro-phenyl-(heptafluoroprop-2-yl)- phenyl- D10 furan-2-yl- 2,6-dimethyl-4- 1.7 (A)544.1 (heptafluoroprop-2-yl)- phenyl- D11 4-trifluoro- 2,6-dimethyl-4-2.0 (A) 638.1 methoxy- (heptafluoroprop-2-yl)- phenyl- phenyl- D124-fluoro-3- 2,6-dimethyl-4- 1.97 (A) 640.1 trifluoromethyl-(heptafluoroprop-2-yl)- phenyl- phenyl- D13 4-trifluoro- 2,6-dimethyl-4-2.0 (A) 622.1 methyl-phenyl- (heptafluoroprop-2-yl)- phenyl- D142-trifluoro- 2,6-dimethyl-4- 1.9 (A) 638.1 methoxy-(heptafluoroprop-2-yl)- phenyl- phenyl- D15 phenyl- 2,6-dimethyl-4- 1.8(A) 554.1 (heptafluoroprop-2-yl)- phenyl- D16 4-fluoro- 2,6-dimethyl-4-1.83 (A) 572.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D17 2-trifluoro-2,6-dimethyl-4- 1.9 (A) 622.1 methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- D18 2-chloro-4- 2,6-dimethyl-4- 1.8 (A) 606.1 fluoro-phenyl-(heptafluoroprop-2-yl)- phenyl- D19 2,3-difluoro- 2,6-dimethyl-4- 1.85(A) 590.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D20 4-methoxy-2,6-dimethyl-4- 1.8 (A) 612.1 carbonyl- (heptafluoroprop-2-yl)- phenyl-phenyl- D21 2-fluoro-5- 2,6-dimethyl-4- 2.0 (A) 640.1 trifluoromethyl-(heptafluoroprop-2-yl)- phenyl- phenyl- D22 2-fluoro- 2,6-diethyl-4-1.96 (A) 600.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D23 2-chloro-2,6-diethyl-4- 2.0 (A) 616.1 phenyl- (heptafluoroprop-2-yl)- phenyl- D244-cyano- 2,6-diethyl-4- 1.9 (A) 607.1 phenyl- (heptafluoroprop-2-yl)-phenyl- D25 4-nitro-phenyl- 2,6-diethyl-4- 2.0 (A) 627.1(heptafluoroprop-2-yl)- phenyl- D26 2-methylthio-4- 2,6-diethyl-4- 2.1(A) 696.1 trifluoromethyl- (heptafluoroprop-2-yl)- phenyl- phenyl- D274-N,N- 2,6-diethyl-4- 2.01 (A) 625.2 dimethylamino-(heptafluoroprop-2-yl)- phenyl- phenyl- D28 5-chloro-2- 2,6-diethyl-4-2.07 (A) 634.1 fluoro-phenyl- (heptafluoroprop-2-yl)- phenyl- D292-chloro-4- 2,6-diethyl-4- 2.0 (A) 661.1 nitro-phenyl-(heptafluoroprop-2-yl)- phenyl- D30 furan-2-yl- 2,6-diethyl-4- 1.83 (A)572.1 (heptafluoroprop-2-yl)- phenyl- D31 4-trifluoro- 2,6-diethyl-4-2.1 (A) 650.1 methyl-phenyl- (heptafluoroprop-2-yl)- phenyl- D322-trifluoro- 2,6-diethyl-4- 2.06 (A) 666.1 methoxy-(heptafluoroprop-2-yl)- phenyl- phenyl- D33 2-methoxy- 2,6-diethyl-4-2.0 (A) 612.2 phenyl- (heptafluoroprop-2-yl)- phenyl- D34 phenyl-2,6-diethyl-4- 1.94 (A) 582.2 (heptafluoroprop-2-yl)- phenyl- D352-trifluoro- 2,6-diethyl-4- 2.0 (A) 650.1 methyl-phenyl-(heptafluoroprop-2-yl)- phenyl- D36 2-chloro-4- 2,6-diethyl-4- 2.0 (A)634.1 fluoro-phenyl- (heptafluoroprop-2-yl)- phenyl- D37 4-methoxy-2,6-diethyl-4- 1.97 (A) 640.2 carbonyl- (heptafluoroprop-2-yl)- phenyl-phenyl- D38 2-fluoro-5- 2,6-diethyl-4- 2.1 (A) 668.1 trifluoromethyl-(heptafluoroprop-2-yl)- phenyl- phenyl- D39 2-fluoro- 2-methoxymethyl-6-2.01 (B) 602.1 phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- D402-methyl- 2-methoxymethyl-6- 2.05 (B) 598.1 phenyl-methyl-4-(heptafluoro- prop-2-yl)-phenyl- D41 2-chloro-2-methoxymethyl-6- 2.0 (B) 618.1 phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- D42 4-cyano- 2-methoxymethyl-6- 2.0 (B) 609.1 phenyl-methyl-4-(heptafluoro- prop-2-yl)-phenyl- D43 4-nitro-phenyl-2-methoxymethyl-6- 2.0 (B) 629.1 methyl-4-(heptafluoro-prop-2-yl)-phenyl- D44 4-methyl- 2-methoxymethyl-6- 2.07 (B) 598.1phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- D45 5-chloro-2-2-methoxymethyl-6- 2.13 (B) 636.1 fluoro-phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- D46 furan-2-yl- 2-methoxymethyl-6- 1.88 (B) 574.1methyl-4-(heptafluoro- prop-2-yl)-phenyl- D47 4-trifluoro-2-methoxymethyl-6- 2.18 (B) 668.1 methoxy- methyl-4-(heptafluoro-phenyl- prop-2-yl)-phenyl- D48 4-fluoro-3- 2-methoxymethyl-6- 2.15 (B)670.1 trifluoromethyl- methyl-4-(heptafluoro- phenyl- prop-2-yl)-phenyl-D49 4-trifluoro- 2-methxoymethyl-6- 2.16 (B) 652.1 methyl-phenyl-methyl-4-(heptafluoro- prop-2-yl)-phenyl- D50 2-trifluoro-2-methoxymethyl-6- 2.11 (B) 668.1 methoxy- methyl-4-(heptafluoro-phenyl- prop-2-yl)-phenyl- D51 2-methoxy- 2-methoxymethyl-6- 2.1 (B)614.1 phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- D52 phenyl-2-methoxymethyl-6- 2.0 (B) 584.1 methyl-4-(heptafluoro-prop-2-yl)-phenyl- D53 4-fluoro- 2-methoxymethyl-6- 2.03 (B) 602.1phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- D54 2-trifluoro-2-methoxymethyl-6- 2.1 (B) 652.1 methyl-phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- D55 2-chloro-4- 2-methoxymethyl-6- 2.1 (B) 636.1fluoro-phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- D56 2-fluoro-5-2-methoxymethyl-6- 2.16 (B) 670.1 trifluoromethyl-methyl-4-(heptafluoro- phenyl- prop-2-yl)-phenyl-

TABLE E Compounds of formula (If): (If)

Comp RT min No. Q¹ Q² (method) MH+ E1 2-fluoro- 2,6-diethyl-4- 2.2 (B)618.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E2 2-methyl-2,6-diethyl-4- 2.3 (B) 614.2 phenyl- (heptafluoroprop-2-yl)- phenyl- E32-chloro- 2,6-diethyl-4- 2.2 (B) 634.1 phenyl- (heptafluoroprop-2-yl)-phenyl- E4 4-cyano- 2,6-diethyl-4- 2.2 (B) 625.1 phenyl-(heptafluoroprop-2-yl)- phenyl- E5 4-nitro-phenyl- 2,6-diethyl-4- 2.23(B) 645.1 (heptafluoroprop-2-yl)- phenyl- E6 4-methyl- 2,6-diethyl-4-2.3 (B) 614.2 phenyl- (heptafluoroprop-2-yl)- phenyl- E7 4-fluoro-2-2,6-diethyl-4- 2.3 (B) 632.1 methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- E8 5-chloro-2- 2,6-diethyl-4- 2.33 (B) 652.1 fluoro-phenyl-(heptafluoroprop-2-yl)- phenyl- E9 2-chloro-4- 2,6-diethyl-4- 2.27 (B)679.1 nitro-phenyl- (heptafluoroprop-2-yl)- phenyl- E10 furan-2-yl-2,6-diethyl-4- 2.12 (B) 590.1 (heptafluoroprop-2-yl)- phenyl- E114-trifluoro- 2,6-diethyl-4- 2.4 (B) 684.1 methoxy-(heptafluoroprop-2-yl)- phenyl- phenyl- E12 4-fluoro-3- 2,6-diethyl-4-2.3 (B) 686.1 trifluoromethyl- (heptafluoroprop-2-yl)- phenyl- phenyl-E13 4-trifluoro- 2,6-diethyl-4- 2.35 (B) 668.1 methyl-phenyl-(heptafluoroprop-2-yl)- phenyl- E14 2-trifluoro- 2,6-diethyl-4- 2.3 (B)684.1 methoxy- (heptafluoroprop-2-yl)- phenyl- phenyl- E15 2-methoxy-2,6-diethyl-4- 2.2 (B) 600.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E16phenyl- 2,6-diethyl-4- 2.2 (B) 618.1 (heptafluoroprop-2-yl)- phenyl- E174-fluoro- 2,6-diethyl-4- 2.3 (B) 668.1 phenyl- (heptafluoroprop-2-yl)-phenyl- E18 2-trifluoro- 2,6-diethyl-4- 2.3 (B) 652.1 methyl-phenyl-(heptafluoroprop-2-yl)- phenyl- E19 2-chloro-4- 2,6-diethyl-4- 2.16 (B)622.1 fluoro-phenyl- (heptafluoroprop-2-yl)- phenyl- E20 4-methyl-2,6-diethyl-4- 2.3 (B) 636.1 [1,2,3]- (heptafluoroprop-2-yl)-thiadiazol-5-yl phenyl- E21 2,3-difluoro- 2,6-diethyl-4- 2.3 (B) 636.1phenyl- (heptafluoroprop-2-yl)- phenyl- E22 2,4-difluoro- 2,6-diethyl-4-2.3 (B) 686.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E23 2-fluoro-2,6-dimethyl-4- 1.9 (A) 590.1 phenyl- (heptafluoroprop-2-yl)- phenyl-E24 2-methyl- 2,6-dimethyl-4- 1.9 (A) 586.1 phenyl-(heptafluoroprop-2-yl)- phenyl- E25 2-chloro- 2,6-dimethyl-4- 1.9 (A)606.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E26 4-cyano-2,6-dimethyl-4- 1.9 (A) 597.1 phenyl- (heptafluoroprop-2-yl)- phenyl-E27 4-methyl- 2,6-dimethyl-4- 2.0 (A) 586.1 phenyl-(heptafluoroprop-2-yl)- phenyl- E28 4-fluoro-2- 2,6-dimethyl-4- 2.0 (A)604.1 methyl-phenyl- (heptafluoroprop-2-yl)- phenyl- E29 5-chloro-2-2,6-dimethyl-4- 2.01 (A) 624.1 fluoro-phenyl- (heptafluoroprop-2-yl)-phenyl- E30 2-chloro-4- 2,6-dimethyl-4- 2.0 (A) 651.1 nitro-phenyl-(heptafluoroprop-2-yl)- phenyl- E31 furan-2-yl- 2,6-dimethyl-4- 1.76 (A)562.1 (heptafluoroprop-2-yl)- phenyl- E32 4-trifluoro- 2,6-dimethyl-4-2.07 (A) 656.1 methoxy- (heptafluoroprop-2-yl)- phenyl- phenyl- E334-fluoro-3- 2,6-dimethyl-4- 2.0 (A) 658.1 trifluoromethyl-(heptafluoroprop-2-yl)- phenyl- phenyl- E34 4-trifluoro- 2,6-dimethyl-4-2.05 (A) 640.1 methyl-phenyl- (heptafluoroprop-2-yl)- phenyl- E352-trifluoro- 2,6-dimethyl-4- 1.95 (A) 656.1 methoxy-(heptafluoroprop-2-yl)- phenyl- phenyl- E36 phenyl- 2,6-dimethyl-4- 1.9(A) 572.1 (heptafluoroprop-2-yl)- phenyl- E37 4-fluoro- 2,6-dimethyl-4-1.9 (A) 590.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E38 2-trifluoro-2,6-dimethyl-4- 2.0 (A) 640.1 methyl-phenyl- (heptafluoroprop-2-yl)-phenyl- E39 2-chloro-4- 2,6-dimethyl-4- 1.9 (A) 624.1 fluoro-phenyl-(heptafluoroprop-2-yl)- phenyl- E40 2,3-difluoro- 2,6-dimethyl-4- 1.9(A) 608.1 phenyl- (heptafluoroprop-2-yl)- phenyl- E41 2,4-difluoro-2,6-dimethyl-4- 1.9 (A) 608.1 phenyl- (heptafluoroprop-2-yl)- phenyl-E42 2-fluoro-5- 2,6-dimethyl-4- 2.04 (A) 658.1 trifluoromethyl-(heptafluoroprop-2-yl)- phenyl- phenyl- E43 2-fluoro- 2-methoxymethyl-6-1.9 (A) 620.1 phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E442-methyl- 2-methoxymethyl-6- 1.9 (A) 616.1 phenyl-methyl-4-(heptafluoro- prop-2-yl)-phenyl- E45 4-cyano-2-methoxymethyl-6- 1.9 (A) 627.1 phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- E46 4-methyl- 2-methoxymethyl-6- 1.94 (A) 616.1phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E47 4-fluoro-2-2-methoxymethyl-6- 1.97 (A) 634.1 methyl-phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- E48 5-chloro-2- 2-methoxymethyl-6- 2.01 (A) 654.1fluoro-phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E49 2-chloro-4-2-methoxymethyl-6- 2.0 (A) 681.1 nitro-phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- E50 furan-2-yl- 2-methoxymethyl-6- 1.75 (A) 592.1methyl-4-(heptafluoro- prop-2-yl)-phenyl- E51 4-trifluoro-2-methoxymethyl-6- 2.06 (A) 686.1 methoxy- methyl-4-(heptafluoro-phenyl- prop-2-yl)-phenyl- E52 4-trifluoro- 2-methoxymethyl-6- 2.04 (A)670.1 methyl-phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E532-trifluoro- 2-methoxymethyl-6- 1.99 (A) 686.1 methoxy-methyl-4-(heptafluoro- phenyl- prop-2-yl)-phenyl- E54 phenyl-2-methoxymethyl-6- 1.9 (A) 602.1 methyl-4-(heptafluoro-prop-2-yl)-phenyl- E55 4-fluoro- 2-methoxymethyl-6- 1.9 (A) 620.1phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E56 2-chloro-4-2-methoxymethyl-6- 2.0 (A) 654.1 fluoro-phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- E57 2,3-difluoro- 2-methoxymethyl-6- 1.93 (A) 638.1phenyl- methyl-4-(heptafluoro- prop-2-yl)-phenyl- E58 2,4-difluoro-2-methoxymethyl-6- 1.9 (A) 638.1 phenyl- methyl-4-(heptafluoro-prop-2-yl)-phenyl- E59 2-fluoro-5- 2-methoxymethyl-6- 2.05 (A) 688.1trifluoromethyl- methyl-4-(heptafluoro- phenyl- prop-2-yl)-phenyl-

TABLE F Compounds of formula (Ic): (Ic)

Comp M.p. No. Q¹ Q² (° C.) F1 phenyl- 2,6-dimethyl-4- 252(heptafluoroprop-2-yl)- phenyl- F2 4-fluoro- 2,6-dimethyl-4- 217 phenyl-(heptafluoroprop-2-yl)- phenyl-

TABLE G Compounds of formula (Id): (Id)

Comp M.p. No. Q¹ Q² (° C.) G1 phenyl- 2,6-diethyl-4- 191(heptafluoroprop-2-yl)- phenyl- G2 4-fluoro- 2,6-diethyl-4- 207 phenyl-(heptafluoroprop-2-yl)- phenyl- G3 4-cyano- 2,6-diethyl-4- 206 phenyl-(heptafluoroprop-2-yl)- phenyl-

Biological Examples

This Example illustrates the pesticidal/insecticidal properties ofcompounds of formula (I).Test against were performed as follows:Spodoptera littoralis (Egyptian Cotton Leafworm):Cotton leaf discs were placed on agar in a 24-well microtiter plate andsprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with 5 L1 larvae. The samples werechecked for mortality, feeding behaviour, and growth regulation 3 daysafter treatment (DAT).The following compounds gave at least 80% control of Spodopteralittoralis: A1, A3, A4, A5, A6, A7, A9, A10, A11, A12, A13, A15, A16,A17, A18, A20, A23, A24, A25, A26, A28, A29, A30, A32, A33, A34, A35,A36, A37, A41, A42, A43, A44, A45, A46, A47, A48, A49, A51, A52, A53,A54, A55, A56, A57, A58, A61, A62, A63, A64, A65, A66, A67, A68, A69,A71, A72, A73, A74, A75, A76, A77, A78, A81, A82, A83, A84, A85, A86,A87, A88, A89, A90, A91, A94, A95, A96, A97, A98, A99, A10, A102, A103,A104, A105, A106, A107, A108, A109, A110, A 111, A112, A114, A115, A116,A117, A118, A120, A121, A122, A123, A124, A125, A126, A127, A128, A134,A135, A136, A137, A138, A139, A142, A143, A144, A145, A146, A147, A148,A151, A152, A154, A155, A156, A157, A158, A159, A162, A163, A164, A165,A166, A167, A168, A169, A175, A176, A178, A179, A180, A182, A183, A184,A186, A187, A188, A189, A190, A191, A192, A194, A195, A196, A197, A198,A199, A200, A205, A206, A209, A210, A211, A212, A213, A214, A215, A216,A217, A218, A219, A220, B1, B3, C1, C2, C3, C4, C5, C6, C8, C9, C10,C11, C12, C13, C14, C15, C16, C17, C18, C19, C21, C24, C25, C26, C27,C29, C30, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, D1, D2, D3,D4, D5, D6, D8, D9, D10, D11, D12, D13, D15, D16, D17, D18, D19, D21,D22, D23, D24, D25, D28, D29, D30, D34, D36, D39, D42, E4, E16, E26,E36, E45, E54, G3.Heliothis virescens (Tobacco Budworm):Eggs (0-24 h old) were placed in 24-well microtiter plate on artificialdiet and treated with test solutions at an application rate of 200 ppm(concentration in well 18 ppm) by pipetting. After an incubation periodof 4 days, samples were checked for egg mortality, larval mortality andgrowth regulation.The following compounds gave at least 80% control of Heliothisvirescens: A1, A4, A9, A13, A16, A20, A23, A25, A32, A33, A34, A35, A36,A37, A41, A42, A43, A44, A45, A46, A47, A48, A49, A51, A52, A53, A54,A55, A56, A57, A58, A61, A62, A63, A64, A65, A66, A67, A68, A69, A71,A72, A73, A74, A75, A76, A77, A78, A80, A81, A82, A83, A84, A85, A86,A87, A88, A89, A90, A91, A92, A94, A95, A96, A97, A98, A99, A100, A10,A102, A103, A104, A105, A106, A107, A108, A109, A110, A 111, A112, A113,A114, A115, A116, A117, A118, A120, A121, A122, A123, A124, A125, A126,A127, A128, A129, A131, A132, A134, A135, A136, A137, A138, A139, A141,A142, A143, A144, A145, A146, A147, A148, A151, A152, A154, A155, A156,A157, A158, A159, A160, A161, A162, A163, A164, A165, A166, A167, A168,A169, A170, A171, A172, A173, A175, A176, A177, A178, A179, A180, A182,A183, A184, A186, A187, A188, A189, A190, A191, A192, A193, A194, A195,A196, A197, A198, A199, A200, A202, A203, A204, A205, A206, A207, A209,A210, A211, A212, A213, A214, A215, A216, A217, A218, A219, A220, B1,B2, B3, B4, B6, B9, B11, B12, C1, C2, C3, C4, C5, C8, C9, C10, C11, C12,C13, C14, C15, C16, C17, C18, C19, C20, C21, C23, C24, C25, C26, C27,C29, C30, C31, C32, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43,D1, D2, D3, D4, D5, D8, D9, D10, D11, D13, D15, D16, D17, D18, D19, D20,D21, D22, D23, D24, D25, D27, D28, D29, D30, D31, D34, D35, D36, D37,D38, D39, D40, D41, D42, D43, D44, D45, D46, D47, D48, D49, D50, D52,D53, D55, E4, E16, E26, E36, E45, E54.Plutella xylostella (Diamond Back Moth):A²⁴-well microtiter plate (MTP) with artificial diet was treated withtest solutions at an application rate of 200 ppm (concentration in well18 ppm) by pipetting. After drying, the MTP's were infested with L2larvae (7-12 per well). After an incubation period of 6 days, sampleswere checked for larval mortality and growth regulation.The following compounds gave at least 80% control of Plutellaxylostella: A1, A3, A4, A5, A6, A7, A8, A9, A11, A12, A13, A15, A16,A17, A18, A20, A23, A24, A25, A26, A29, A30, A31, A32, A33, A34, A35,A36, A37, A41, A42, A43, A44, A45, A46, A47, A48, A50, A51, A52, A53,A54, A55, A56, A58, A61, A62, A63, A64, A65, A66, A67, A68, A69, A71,A72, A73, A74, A75, A76, A77, A78, A81, A82, A83, A84, A85, A87, A88,A89, A90, A91, A94, A95, A96, A97, A98, A99, A10, A102, A103, A104,A105, A106, A107, A108, A109, A110, A 111, A112, A114, A115, A116, A117,A118, A121, A122, A123, A124, A125, A126, A127, A128, A129, A131, A132,A134, A135, A136, A137, A138, A139, A141, A142, A143, A144, A145, A146,A147, A148, A149, A151, A152, A154, A155, A156, A157, A158, A159, A160,A161, A162, A163, A164, A165, A166, A167, A168, A169, A171, A172, A175,A176, A177, A178, A179, A180, A182, A183, A186, A187, A188, A189, A190,A191, A192, A193, A194, A195, A196, A197, A198, A199, A200, A202, A203,A205, A206, A207, A209, A210, A211, A212, A213, A214, A215, A216, A217,A218, A219, A220, B1, B2, B3, B11, B12, C1, C2, C3, C4, C5, C6, C8, C9,C11, C12, C13, C16, C17, C18, C19, C20, C21, C24, C25, C26, C27, C29,C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C41, C42, C43, D1, D2,D3, D4, D5, D8, D9, D11, D12, D13, D15, D16, D17, D18, D19, D21, D22,D23, D24, D25, D27, D28, D29, D30, D31, D34, D36, D38, D47, D48, D49,D52, D53, D55, D56, E4, E16, E26, E36, E45, E54.Diabrotica balteata (Corn Root Worm):A²⁴-well microtiter plate (MTP) with artificial diet was treated withtest solutions at an application rate of 200 ppm (concentration in well18 ppm) by pipetting. After drying, the MTP's were infested with larvae(L2) (6-10 per well). After an incubation period of 5 days, samples werechecked for larval mortality, and growth regulation.The following compounds gave at least 80% control of Diabroticabalteata: A1, A3, A4, A5, A6, A8, A9, A11, A12, A13, A15, A16, A17, A18,A20, A23, A24, A25, A26, A28, A29, A30, A31, A32, A33, A34, A35, A36,A37, A41, A42, A43, A44, A46, A47, A48, A51, A52, A53, A54, A55, A56,A58, A61, A62, A63, A64, A65, A66, A67, A68, A69, A71, A72, A73, A74,A75, A76, A77, A78, A80, A81, A82, A83, A84, A85, A86, A87, A89, A90,A91, A92, A94, A95, A96, A97, A98, A99, A10, A110, A102, A103, A104,A105, A106, A107, A108, A109, A110, A111, A112, A114, A115, A116, A117,A118, A120, A121, A122, A123, A124, A125, A126, A127, A128, A129, A131,A132, A134, A135, A136, A137, A138, A139, A141, A142, A143, A144, A145,A146, A147, A148, A149, A151, A152, A154, A155, A156, A157, A158, A159,A162, A162, A163, A164, A165, A166, A167, A168, A169, A171, A172, A175,A176, A177, A178, A179, A180, A181, A182, A183, A186, A187, A188, A189,A190, A191, A192, A193, A194, A196, A198, A199, A200, A202, A206, A207,A210, A211, A212, A213, A214, A215, A216, A217, A218, A219, B1, B4, B6,B9, B11, B12, C1, C2, C4, C5, C6, C8, C9, C11, C12, C13, C16, C17, C19,C21, C23, C24, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36,C37, C38, C39, C40, C41, C42, C43, D1, D2, D3, D4, D5, D8, D9, D11, D12,D15, D16, D17, D18, D19, D22, D23, D24, D25, D27, D28, D29, D31, D34,D36, D38, D42, D45, D47, D49, D52, D53, D55, E4, E16, E26, E36, E45,E54.Myzus persicae (Green Peach Aphid):Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with an aphid population of mixedages. After an incubation period of 6 DAT, samples were checked formortality.The following compounds gave at least 80% control of Myzus persicae: A1,A41, A42, A43, A44, A45, A46, A48, A51, A52, A53, A54, A55, A58, A62,A63, A64, A66, A68, A71, A72, A74, A75, A76, A81, A103, A104, A105,A114, A122, A142, A143, A154, A176, A189, A190, A192, A194, A195, A210,A211, A212, A213, A215, A216, A218, C41.Thrips tabaci (Onion Thrips):Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with an aphid population of mixedages. After an incubation period of 7 days, samples were checked formortality.The following compounds gave at least 80% control of Thrips tabaci: A3,A4, A15, A24, A25, A26, A32, A33, A34, A35, A41, A42, A43, A44, A45,A46, A47, A48, A51, A52, A53, A54, A55, A57, A61, A62, A63, A64, A65,A66, A67, A68, A71, A72, A73, A74, A75, A76, A77, A82, A83, A85, A87,A91, A94, A95, A97, A98, A99, A102, A103, A104, A105, A107, A108, A109,A111, A114, A115, A116, A117, A118, A122, A123, A124, A125, A127, A134,A135, A137, A138, A142, A143, A144, A145, A146, A147, A148, A149, A151,A154, A155, A156, A157, A158, A160, A162, A162, A167, A168, A176, A182,A183, A187, A188, A189, A190, A191, A192, A194, A195, A196, A197, A198,A199, A210, A211, A212, A213, A215, A216, A218, A219, C17, C24, C25,C26, C27, C29, C30, C35, C36, C38, C39, C41, D4, D5, D9, D22, D24, D25,D29, D34, D36, D39, D40, D44, D52, D53, E16, E54.Tetranychus urticae (Two-Spotted Spider Mite):Bean leaf discs on agar in 24-well microtiter plates were sprayed withtest solutions at an application rate of 200 ppm. After drying, the leafdiscs are infested with mite populations of mixed ages. 8 days later,discs are checked for egg mortality, larval mortality, and adultmortality.The following compounds gave at least 80% control of Tetranychusurticae: A1, A4, A5, A6, A11, A13, A16, A17, A18, A23, A24, A26, A34,A42, A43, A44, A52, A54, A55, A62, A63, A64, A65, A66, A68, A71, A72,A73, A74, A75, A77, A82, A83, A84, A85, A87, A88, A89, A91, A94, A95,A96, A97, A98, A99, A102, A103, A104, A105, A107, A108, A110, A114,A115, A116, A117, A122, A123, A124, A125, A127, A135, A137, A138, A142,A143, A144, A147, A155, A157, A158, A164, A165, A166, A167, A168, A171,A175, A176, A177, A179, A182, A183, A186, A187, A188, A189, A190, A191,A192, A194, A195, A197, A198, A199, A200, A205, A206, A207, A209, A210,A211, A212, A213, A214, A215, A216, A218, A219, A220, C5, C9, C25, C27,C30, C34, C36, C40, C42, C43, D1, D2, D3, D4, D5, D6, D8, D9, D17, D18,D24, D25, D29, D36, D42, D53, D55, E26, E36, E54.

1. A compound of formula (I):

wherein A¹, A², A³ and A⁴ are independently of one another C—R³, C—R⁵ ornitrogen, provided that at least one of A¹, A², A³ and A⁴ is C—R³ and nomore than two of A¹, A², A³ and A⁴ are nitrogen; R¹ and R² areindependently of each other hydrogen, C₁-C₄alkyl, C₂-C₄alkenyl,C₂-C₄alkynyl, C₁-C₄alkylcarbonyl, hydroxy, C₁-C₄alkylcarbonyloxy,arylcarbonyloxy or arylcarbonyloxy wherein the aryl ring is substitutedby one to five substituents independently selected from halogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy; G¹ and G²are independently of each other oxygen or sulfur; each R³ isindependently cyano, thiocyanato, aminothiocarbonyl,N—C₁-C₄alkyl-aminothiocarbonyl or N,N-di-C₁-C₄alkyl-aminothiocarbonyl;each R⁵ is independently hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkylor C₁-C₄alkoxy; Q¹ is aryl or aryl substituted by one to fivesubstituents R⁶, which may be the same or different, or Q¹ isheterocyclyl or heterocyclyl substituted by one to five substituents R⁶,which may be the same or different; wherein each R⁶ is independentlycyano, nitro, hydroxy, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₄alkoxy-C₁-C₄-alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₄alkoxy-C₁-C₄-alkoxy, C₁-C₆alkylthio,C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, N—C₁-C₆alkylamino,N,N-di-(C₁-C₆alkyl)amino, N,N-di-(C₁-C₆alkyl)aminocarbonyl,N,N-di-(C₁-C₆alkyl)aminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonylamino,aryl or aryl which is substituted by one to five substituentsindependently selected from cyano, nitro, hydroxy, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy, or heteroaryl orheteroaryl which is substituted by one to five substituentsindependently selected from cyano, nitro, hydroxy, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; and Q² is a moiety offormula (II) or (III)

wherein Y¹ and Y⁵ are independently of each other cyano, halogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy-C₁-C₄-alkyl, C₁-C₃alkylthio,C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl,C₁-C₃alkylsulfonyl or C₁-C₃haloalkylsulfonyl; Y³ is C₂-C₆perfluoroalkyl, C₁-C₆ perfluoroalkylthio, C₁-C₆ perfluoroalkylsulfinylor C₁-C₆ perfluoroalkylsulfonyl; Y² and Y⁴ are independently of eachother hydrogen, halogen or C₁-C₄alkyl; Y⁶ and Y⁹ are independently ofeach other cyano, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy-C₁-C₄-alkyl, C₁-C₃alkylthio, C₁-C₃haloalkylthio,C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl orC₁-C₃haloalkylsulfonyl; Y⁸ is C₁-C₄haloalkoxy, C₂-C₆ perfluoroalkyl,C₁-C₆ perfluoroalkylthio, C₁-C₆ perfluoroalkylsulfinyl or C₁-C₆perfluoroalkylsulfonyl; Y⁷ is hydrogen, halogen or C₁-C₄alkyl; or a saltor N-oxide thereof.
 2. A compound according to claim 1 wherein A¹ isC—R³ or C—R⁵.
 3. A compound according to claim 1 wherein A² is C—R³ orC—R⁵.
 4. A compound according to claim 1 wherein A³ is C—R³ or C—R⁵. 5.A compound according to claim 1 wherein A⁴ is C—R³ or C—R⁵.
 6. Acompound according to claim 1 wherein one, two or three of A¹, A², A³and A⁴ are C—R³.
 7. A compound according to claim 1 wherein R¹ ishydrogen, methyl, ethyl, allyl, propargyl, acetyl, hydroxy, acetyloxy orbenzoyloxy.
 8. A compound according to claim 1 wherein R² is hydrogen,methyl, ethyl, allyl, propargyl, acetyl, hydroxy, acetyloxy orbenzoyloxy.
 9. A compound according to claim 1 wherein G¹ is oxygen. 10.A compound according to any claim 1 wherein G² is oxygen.
 11. A compoundaccording to claim 1 wherein each R³ is independently cyano, thiocyanatoor aminothiocarbonyl.
 12. A compound according to claim 1 wherein eachR⁵ is independently hydrogen, fluoro, chloro, bromo, methyl,trifluoromethyl or methoxy.
 13. A compound according to claim 1 whereinQ¹ is aryl or aryl substituted by one to five substituents R⁶, which maybe the same or different, or Q¹ is heteroaryl or heteroaryl substitutedby one to five substituents R⁶, which may be the same or different. 14.A compound according to claim 1 wherein Q² is a moiety of formula (II).15. A compound of formula (XIII)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in claim 1; or asalt or N-oxide thereof, or a compound of formula (IX′)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in claim 1; or asalt or N-oxide thereof, or a compound of formula (IX)

wherein A¹, A², A³, A⁴, R¹, R², G² and Q² are as defined in claim 1; ora salt or N-oxide thereof, or a compound of formula (XI)

wherein A¹, A², A³, A⁴, R², G² and Q² are as defined in claim 1 and LGis a leaving group; or a salt or N-oxide thereof.
 16. A method ofcombating and controlling insects, acarines, nematodes or molluscs whichcomprises applying to a pest, to a locus of a pest, or to a plantsusceptible to attack by a pest an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound offormula (I) as defined in claim
 1. 17. An insecticidal, acaricidal ornematicidal composition comprising an insecticidally, acaricidally ornematicidally effective amount of a compound of formula (I) as definedin claim 1.